JPH07120935A - Alkaline developer for radiation sensitive composition - Google Patents

Abstract

PURPOSE:To obtain a picture element or a resist film having a sharp pattern edge without generating scum, film residue, etc., by using an alkaline aq. soln. of a specified pH contg. a specified amt. of a nonionic surfactant. CONSTITUTION:This alkaline developer is an aq. soln. of pH9-13 contg. an alkaline compd. and 0.01-1.0wt.% nonionic surfactant. Any of inorg. and org. alkaline compds. may be used as the alkaline compd. The nonionic surfactant is preferably polyoxyethylene allyl ether, polyoxyethylene alkyl ether, polyoxyethylene alkylallyl ether or a polyoxyethylene deriv.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an alkaline developer for a radiation-sensitive composition, and more particularly, when forming a resist film on an integrated circuit, a printed circuit board or the like, or in a color liquid crystal device or an image pickup tube element. The present invention relates to an alkaline developer used for developing a coating film formed from a radiation-sensitive composition when forming a color filter for use in the same.

[0002]

2. Description of the Related Art Conventionally, a resist film which has been widely used in the field of fine processing such as an integrated circuit, a printed circuit board, a color filter is usually coated with a radiation-sensitive composition for forming a resist film. Form a film, irradiate this coating film with radiation, then develop with an alkaline developer,
It is manufactured by removing unnecessary portions of the coating film to form a pattern shape.

The development of a coating film made of such a radiation-sensitive composition is carried out by a method such as dip development, swing development, dip development, shower spray development, puddle development, etc. , An alkaline developer is used.

Conventionally, as such an alkaline developing solution, a 2 to 3% by weight aqueous solution of tetramethylammonium hydroxide has been widely used.

[0005]

The conventional alkaline developer as described above dissolves an organic substance having a relatively small molecular weight such as a photoresist film composed of a novolac resin and a naphthoquinonediazide type photosensitizer. Is designed.

However, using such a conventionally known developing solution, a radiation-sensitive composition containing a binder polymer having a relatively large molecular weight and a radiation-sensitive compound, in which pigments or fine particles are dispersed, for example, a color-sensitive composition for color filters. When a coating film made of a radioactive composition or a silica particle-dispersed radiation sensitive composition for an interlayer film is developed to form a resist film or a color filter, an unnecessary coating film cannot be sufficiently dissolved and removed. There was an occasion. That is, there is a problem that particles or undissolved substances are likely to remain in the non-formed portion of the resist film, scum, background stain, and film residue are generated, and a resist pattern or pixel having a sharp pattern edge cannot be formed. there were.

For this reason, conventionally, the alkali concentration of the developing solution has been increased or the development has been carried out while giving a mechanical stimulus. However, in this case, a necessary resist film may be peeled off, for example, a color film. In the manufacture of the filter, the pixel portion was sometimes omitted.

Therefore, when a coating film formed of a radiation-sensitive composition in which pigments or fine particles are dispersed is developed to produce a resist pattern or a color filter, the unnecessary coating film is dissolved without peeling of the film. An alkaline developer for a radiation-sensitive composition that can be removed and can form a resist pattern or a color filter having a sharp pattern edge without causing scum, background stain, film residue, and the like. Was expected.

[0009]

The present inventors have found that the alkaline development for a radiation-sensitive composition, which is an alkaline aqueous solution having a pH in a specific range and containing a nonionic surfactant in a specific amount. The present inventors have completed the present invention by finding that the liquid can solve the above problems.

[0010]

DETAILED DESCRIPTION OF THE INVENTION The alkaline developer for radiation-sensitive composition according to the present invention will be described in detail below.

The alkaline developer for radiation-sensitive composition according to the present invention is an aqueous solution containing [A] an alkaline compound and [B] a nonionic surfactant,
(i) It has a pH of 9 to 13, and (ii) contains the above-mentioned nonionic surfactant in an amount of 0.01 to 1.0% by weight.

First, the components [A] and [B] will be described. [A] Alkaline Compound In the present invention, both an inorganic alkaline compound and an organic alkaline compound can be used as the alkaline compound.

Specific examples of the inorganic alkaline compound used in the present invention include lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium hydrogen phosphate, diammonium hydrogen phosphate, dipotassium hydrogen phosphate, hydrogen phosphate. Disodium, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium dihydrogen phosphate, lithium silicate, sodium silicate, potassium silicate, lithium carbonate, sodium carbonate, potassium carbonate, lithium borate,
Examples thereof include sodium borate, potassium borate, and ammonia.

Specific examples of the organic alkaline compound include tetramethylammonium hydroxide and hydroxide.
2-hydroxyethyltrimethylammonium, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopyramine, diisopyramine, ethanolamine and the like can be mentioned.

Of these, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, trimethylhydroxyethylammonium hydroxide and the like are preferable.

These may be used in combination of two or more kinds. [C] Nonionic Surfactant Specific examples of the nonionic surfactant (nonionic surfactant) used in the present invention include polyoxyethylene alkyl ether, polyoxyethylene allyl ether, and polyoxyethylene alkyl. Allyl ether, polyoxyethylene derivative, oxyethylene / oxypropylene block copolymer, sorbitan fatty acid ester,
Polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester,
Examples thereof include polyoxyethylene alkylamine.

Of these, polyoxyethylene allyl ether, polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene derivative and the like are preferable.

These may be used in combination of two or more. Other components The alkaline developer for radiation-sensitive composition according to the present invention,
When residual ions, residual salts, etc. do not pose a problem to the resulting resist film or color filter, an anionic surfactant or a cationic surfactant may be added as necessary within the range not impairing the object of the present invention. May be.

As such an anionic surfactant,
Specifically, higher alcohol sulfate ester salts such as sodium lauryl alcohol sulfate ester, sodium oleyl alcohol sulfate ester, alkyl sulfate salts such as sodium lauryl sulfate and ammonium lauryl sulfate, alkyl dodecylbenzenesulfonate, sodium dodecylnaphthalenesulfonate, etc. Aryl sulfonates etc. are mentioned.

Specific examples of the cationic surfactant include quaternary ammonium salts such as stearylamine hydrochloride, lauryltrimethylammonium chloride and alkylbenzenedimethylammonium chloride.

Alkaline developer for radiation-sensitive composition The alkaline developer for radiation-sensitive composition according to the present invention comprises
An aqueous solution containing the above alkaline compound [A] and a nonionic surfactant [B], wherein (i) the pH is 9 to
13 and (ii) contains the above-mentioned nonionic surfactant in an amount of 0.01 to 1.0% by weight.

The pH of the alkaline developer for the radiation-sensitive composition is 9 to 13 depending on the alkaline compound [A],
It is particularly preferably adjusted to 10.0 to 12.5.
Further, the alkaline developer for radiation-sensitive composition according to the present invention contains the nonionic surfactant [B] at 0.0% as described above.
It is contained in an amount of 1 to 1.0% by weight, particularly preferably 0.05 to 0.5% by weight.

When the coating film formed from the radiation-sensitive composition is developed using the alkaline developer for radiation-sensitive composition according to the present invention, the resist film is not peeled off and unnecessary. The coating film can be sufficiently dissolved and removed, and scum and film residue do not occur. Therefore, a pixel (color filter) or a resist film having a sharp pattern edge can be formed.

The alkaline developer having a pH of less than 9 is
A film residue is likely to occur, while an alkaline developer having a pH of more than 13 may cause a necessary resist film such as pixels to be missing or film peeling.

In the alkaline developer, if the content of the nonionic surfactant is less than 0.01% by weight, scum and film residue are likely to occur, while if it exceeds 1.0% by weight, the amount of the developer is increased. Foaming is likely to occur and the developing workability may be deteriorated.

When the alkaline developer for radiation-sensitive composition according to the present invention is used, even when a coating film of the radiation-sensitive composition in which fine particles such as silica particles and pigments are dispersed is developed,
No fine particles or undissolved matter remains, no pixels are lost, and no peeling of the resist film occurs.

The alkaline developer for a radiation-sensitive composition according to the present invention as described above is used, for example, when forming a color filter from a radiation-sensitive resin composition for a color filter having the following composition or in a resist. It is preferably used when forming a resist film from the radiation-sensitive resin composition for film formation.

Such a radiation-sensitive resin composition for a color filter is usually one in which an organic or inorganic pigment, an alkali-soluble binder polymer and a radiation-sensitive compound are dissolved or dispersed in an organic solvent.

Specific examples of the alkali-soluble binder polymer include methyl methacrylate / vinyl phenol / styrene / methacrylic acid copolymer, benzyl methacrylate / methacrylic acid / styrene copolymer, methyl methacrylate / methacrylic acid / styrene copolymer. Polymer,
Examples thereof include benzyl methacrylate / methacrylic acid / polystyrene macromonomer copolymer and methyl methacrylate / methacrylic acid / polystyrene macromonomer copolymer.

The molecular weight of such a binder polymer is usually 5,000 to 200,000, preferably 2,000.
It is preferably 0 to 80,000. The radiation-sensitive compound is a compound which, when irradiated with radiation, produces radicals (active molecular fragments) such as carbene and nitrene to react with each other, and causes the binder polymer to form a three-dimensional crosslinked structure.
Specific examples include a photopolymerization initiator, a photopolymerizable monomer, a photopolymerizable oligomer, and a photocrosslinking agent.

The radiation-sensitive resin composition for a color filter as described above may contain a pigment or fine particles as described above. In the present invention, the term "radiation" is meant to include ultraviolet rays, electron beams, X-rays and the like.

[0032]

EXAMPLES Next, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.

The composition of the pigment-dispersed resist for color filters used in the following examples is shown in Table 1.

[0034]

[Table 1]

[0035]

[Example 1] On a soda glass substrate surface (5 cm) on which a SiO ₂ film for preventing elution of sodium ions was formed
A light-shielding layer having a pattern shape of 20 μm × 20 μm is formed in a size of 5 cm, and the pigment-dispersed resist for a color filter shown in Table 1 is applied to a desired thickness (1.5
μm) and then the resulting coating film was prebaked at 80 ° C. for 10 minutes to obtain a dry coating film.

The dried coating film was then exposed to 100 mj / cm ² of ultraviolet light through a photomask with a high pressure mercury lamp. On the other hand, an alkaline developing solution was prepared from each component as shown in Table 2. To an amount of 1000 g of water in which an amount of the nonionic surfactant as shown in Table 2 was dissolved, a 20 wt% aqueous solution of the alkaline compound shown in Table 2 was added to adjust the pH to 1
An alkaline developer was prepared by adjusting the ratio to 1.3.

The alkaline developer 2 thus prepared
Using 00 g, one substrate having the dry coating film obtained as described above was dipped and developed while gently rocking. After development, the substrate was rinsed with pure water, and when the pixels formed on the substrate were observed with a microscope, pixels were not missing and pixels with sharp pattern edges were formed. There was no scum or film residue on the top.

[0038]

Example 2 An alkaline developer having a pH of 10.5 was prepared in the same manner as in Example 1 from the components shown in Table 2.
A dry coating film was formed and developed in the same manner as in Example 1 except that this alkaline developer was used.

When the obtained pixel was observed with a microscope,
Pixels were not missing, pixels having sharp pattern edges were formed, and there was no scum or film residue on the non-pixel substrate.

[0040]

Example 3 An alkaline developer having a pH of 12.0 was prepared in the same manner as in Example 1 from the components shown in Table 2.
A dry coating film was formed and developed in the same manner as in Example 1 except that this alkaline developer was used.

Observation of the obtained pixels with a microscope revealed that
Pixels were not missing, pixels having sharp pattern edges were formed, and there was no scum or film residue on the non-pixel substrate.

[0042]

Comparative Example 1 A dry coating film was formed in the same manner as in Example 1 except that an alkaline developer having a pH of 11.5 as shown in Table 2 containing no nonionic surfactant was used. And developed.

When the obtained pixel was observed with a microscope,
Pixels were not missing, but the pattern edges were not sharp and scum was observed.

[0044]

Comparative Example 2 An alkaline developer having a pH of 10.6 was prepared in the same manner as in Example 1 from the components shown in Table 2.
A dry coating film was formed and developed in the same manner as in Example 1 except that this alkaline developer was used.

When the obtained pixel was observed with a microscope,
Pixels were not missing, but film residue was found on the non-pixel substrate.

[0046]

Comparative Example 3 An alkaline developing solution having a pH of 8.5 was prepared from each component shown in Table 2 in the same manner as in Example 1. A dry coating film was formed and developed in the same manner as in Example 1 except that this alkaline developer was used.

When the obtained pixel was observed with a microscope,
A film residue was remarkably seen on the non-pixel substrate, and a sharp pattern was not obtained.

[0048]

Comparative Example 4 An alkaline developing solution having a pH of 13.5 was prepared from each component shown in Table 2 in the same manner as in Example 1.
A dry coating film was formed and developed in the same manner as in Example 1 except that this alkaline developer was used.

When the obtained pixel was observed with a microscope,
Pixel loss was observed.

[0050]

[Table 2]

[0051]

As described above, when a resist pattern or a color filter is formed by developing a coating film using the alkaline developer for radiation-sensitive composition according to the present invention,
Peeling does not occur, and unnecessary coatings can be sufficiently dissolved and removed, and pixels (color filters) or resist films with sharp pattern edges can be formed without scum or film residue. can do.

Such an alkaline developer for radiation-sensitive composition according to the present invention comprises a radiation-sensitive composition containing a high molecular weight binder polymer and fine particles such as silica particles and pigments dispersed therein. It is also preferably used when developing a film.

Claims (1)

[Claims] 1. An aqueous solution containing [A] an alkaline compound and [B] a nonionic surfactant, wherein (i) the pH is 9 to 13, and (ii) the above nonionic surfactant. In an amount of 0.01 to 1.0% by weight, an alkaline developer for a radiation-sensitive composition.