JPS5872142A - Processing method for lippmann type photosensitive silver halide material - Google Patents

Abstract

PURPOSE:To obtain a mask with high resolving power and accuracy for manufacturing a minute integrated circuit by adding an org. compound having a specified value or above of solubility product with Ag<+> to a cleaning bath contg. SO<-2>3 at a specified concn. in the reversal of a Lippmann type photosensitive silver halide material. CONSTITUTION:In the reversal of a Lippmann type photosensitive silver halide material contg. silver halide particles having <=100nm average particle size, >=1 kind of org. compound (formula 1-4) showing >=11.8 solubility product with Ag<+> at 25 deg.C is added to a cleaning bath contg. >=0.08mol/l SO<-2>3 behind a bleaching bath. By making use of the resulting processing bath, a stable image with high resolution and sharpness for manufacturing a mask used in the electronic industry is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for processing a Tubmann type silver halide photographic light-sensitive material, and more particularly to a reversal processing method for the above-mentioned light-sensitive material which is excellent in #* density and reproducibility. Lippmann emulsions, in which the average grain size of the silver halide grains is usually less than 100:am, are used for the production of photographic plates or films with high resolving power V, for use in microphotography, for recording nuclear physical phenomena. , manufacturing of masks during the manufacturing of microelectronic integrated circuits,
Costs are important, such as for use in the Hopglare method for high-density data storage.

In manufacturing microelectronic integrated circuits, a highly enlarged drawing of the various continuous masks needed to make one integrated circuit is created, and then this drawing is reduced in successive steps if necessary, and then photographed. They are reproduced on Lippmann plates or films to form masks for integrated circuits. By various photographic and chemical processes (photoetching of lacquered plates), the images of the masks thus produced can be used to visualize the required circuit elements. The integrated circuit is transferred to the surface on which the integrated circuit is made.

The photographic material used in manufacturing the above masks must have high resolution and precision, and must be capable of accurately reproducing the resolution of the image.

However, such a Lippmann-layer halogenated chain photographic light-sensitive material in which a Lippmann emulsion layer having high resolution is formed on a support encounters special problems as described below when subjected to reversal processing.

The above-mentioned reversal process means that after the photosensitive material that has been exposed to light is exposed to light, the formed silver is bleached and decentered, and the silver halide that was not subjected to WILgII is exposed to light again to produce a second photosensitive material.
A photographic processing method for obtaining a positive image by
This is a photographic processing method known to those skilled in the art, which is described in pages 69 to 71 of "Science Photograph Handbook" published by Maruso.

When the Lippmann type silver halide photographic light-sensitive material is processed by the above reversal processing method, fewer silver halide emulsion grains are to be developed in the second development, resulting in a decrease in the density of the developed image. When such a photosensitive material is used, it is extremely difficult to print a pattern that is identical to the one on the silicone. Moreover, the image obtained by reversal development is inferior to the original image in terms of sharpness, and the edges of the image become rounded, and the reproducibility of line width is poor, resulting in thin reproduction. .

According to the present inventor, it has been found that such a phenomenon occurs particularly when silver oxide emulsion grains disappear to a large extent in the cleaning bath of the reversal process, and furthermore, when the grain size is larger, It has also been found that this is a property unique to the Lippmann type emulsion, since it cannot occur in emulsions containing silver halide grains having the same characteristics.

An object of the present invention is to provide a method for processing a Lippmann-based silver halide photographic light-sensitive material in which silver halide emulsion grains are not lost during cleaning in the reversal processing step.
Another object of the present invention is to provide a reversal processing method in which both image density and image reproducibility are improved.

As a result of various studies, the inventors of the present invention have determined that, in the reversal processing method for silver saponide photosensitive materials, the above-mentioned objective is to provide silver ions in a cleaning solution containing at least 0.08 mol/j of sulfite ions following a bleaching bath. Solubility product (Pl:s
)) It has been found that this can be achieved by a method of processing a Lippmann-type silver oxide photographic light-sensitive material in which at least one organic compound exhibiting 11.8 or more is added at 25°C.

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

In the treatment method of the present invention, a cleaning bath is used as a treatment bath following the bleaching bath, and organic compounds having a solubility product with silver ions of 11.8 or more at 25°C are added to the cleaning bath. Compounds represented by the following general formula (1) or (b) are preferably used.

General formula (1) General formula (2) In the above formula, 2 represents an atomic group necessary to form a 5- or 6-membered heterocycle.

Specific examples of the 5- or 6-membered heterocycle formed by 2 above include a tetrazole ring (e.g., 1-phenyltetrazole ring, etc.), thiadiazole II (e.g., 1-phenyltetrazole ring, etc.), thiadiazole II (e.g.,
, 3,4-thiadiazole ring, etc.), oxadiazole II (e.g., 1,3,4-oxadiazole ring, etc.),
Thiazole II (e.g. benzothiazole ring etc.), selenazole ring, oxazole II (e.g. benzoxazole ring etc.), imidazole ring (e.g. benzimidazole ring etc.), triazole II (e.g. 4-7enyl-1.2.4-) lyazole ring ), biridine ring, etc. These heterocyclic groups include those substituted with an amine group, an alkyl group, a cycloalkyl group, an aryl group, an acyl group, etc. at an appropriate position.

Specific examples of the compounds represented by the above general formula will be described below.

(Compound examples) (1) (3) (odor (4) (5) (9)(
7) (11) Conventionally,
By adding the above-mentioned compound known as an anti-capri agent to a cleaning bath for reversal processing containing sulfite as a main component, the image reproducibility during the second development of Lippmann type silver halide photographic light-sensitive materials can be improved. This was discovered for the first time by the present invention.

The above compound is dissolved in any solvent such as methanol, ethanol, a mixed solvent of water and methanol, etc., and added to the cleaning bath. At that time, the amount added is 1 per 11 clean baths.
A range of 0 to tp is preferable.O In the present invention, the above-mentioned cleaning bath may contain known components, such as alkali metal salts of sulfite and alkali metal salts of bisulfite, either alone or in combination. It is generally preferred that the concentration of sulfite ions in the bath is 0.08 mol or more per liter of bath. This cleaning bath may also contain a silver halide solvent such as thiosulfate, and a metal chelating agent such as anobolycarboxylic acid, a salt thereof, or a polyphosphate. is arbitrary, but preferably about PH3-9.

The reversal process in the present invention basically consists of the following steps.

(1) First development, (2) Development stop, (Bleaching, (4) Cleaning, (5) Second exposure, (6) Second development, (7) Fixing, (
8) Washing with water ℃・Clean, (9) Washing with water, GO) Drying Depending on the case, among the above steps, (2), (7), (
At least one step of 9) can be omitted. Also, there is no problem in adding water washing between each process.

The photosensitive material used in the reversal process of the present invention is imaged by a method depending on the use of the photosensitive material. The exposed photosensitive material is developed to obtain a negative image, and this is usually called first development. After the developed silver from the first development is oxidized and removed in a bleach bath, all remaining silver halide is developed.
This is called second development. The developer used in the first development and second development is an alkaline aqueous solution containing a developing agent. Dihydroxybenzene IINFI, which is generally well known to the person in question, includes hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, toluhydroquinone, methylhydroquinone, 2,3-diku-p-stohydroquinone, 2,5-dimethylhydroquinone, etc. ), 3-pyrazolidones (e.g. 1-7enyl-3-pyrazolidone, 1-7enyl-4
-Methyl-3-pyrazolidone, 1-phenyl-4,4-
Dimethyl-3-pyrazolidone, 1-phenyl-4-ethyl-3-pyrazolidone, 1-phenyl-5-methyl-3
-pyrazolidones, etc.), ami/phenols (e.g. 0
-Aminophenol, 7-ethyl, p-aminophenol, methyl-P-aminophenol, methyl-P-aminophenol, 2゜4-diaminophenol, etc.), Piwagapol, ascorbic acid, 1-aryl -3-aminopyrazoline-3-aminopyrazolines (e.g. 1-(p-
hydroxyphenyl)-3-aminopyrazoline, 1-(
p-Methylaminophenol)-3-aminopyrazoline, 1(p-amino-m-methylphenyl)-3-aminopyrazolinetxt), p-phenylenediamines (e.g. 4-amino-N,N-diethyl Aniline, 3-
Methyl-4-amino-M, N-diethylaniline, 4-
Amino-ethyl-β-hydroxyethylaniline, 3-methy/L-4-amino-U-ethyl-β
-methanesulfamide ethylaniline, 4-amino-3
-Methyl-U-ethyl-■-β-methoxyethylaniline, etc.) or a mixture thereof.The developer may also contain preservatives (e.g. sulfite, bisulfite, etc.), buffers ( (e.g. carbonates, boric acid, borates, phosphates, alkanolamines, etc.), alkaline agents (e.g. hydroxides, carbonates, phosphates, etc.), solubilizing agents (e.g. polyethylene glycols, esters thereof, etc.), pi (regulators (e.g. acetic acid), sensitizers (e.g. quaternary ammonium salts), development accelerators, surfactants, anti-capri agents (e.g. potassium bromide, sodium bromide, benzotriazole, benzothiazole, tetrazole, thiazole, etc.), chelating agents (for example, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid or salts thereof, polyphosphates, etc.), and the like.

The development stop bath has the effect of not only obtaining a desired development result by promptly stopping the development reaction, but also preventing a decrease in the bleaching bath performance due to the developer being brought into the bleaching process.

For this purpose, in addition to simple water, aqueous solutions such as sulfuric acid, hydrochloric acid, acetic acid, and citric acid are used.

The purpose of the bleaching solution is to neutralize the alkalinity of the developing solution. The bleaching solution used has a composition that has oxidizing power against the silver. In other words, permanganates, persulfurates, dichromates, red blood salts, ceric salts, ferric rings, cupric salts, metal complexes of aminopolycarboxylic acids, etc. may be used alone or in combination. It is used as

The fixing solution is a processing solution used for the purpose of dissolving and removing undeveloped silver halide. For this purpose, silver halide solvents such as thiosulfates such as aluminum thiosulfate and sodium thiosulfate, thiourea, and amine derivatives are used as main components, and silver halide solvents such as ammonium sulfite, sodium sulfite, sodium bisulfite, potassium metabisulfite, etc. sulfites, boric acid,
Borates such as borax, metaboric acid), organic carboxylic acids such as acetic acid, citric acid, tartaric acid, malic acid, inorganic salts such as sulfuric acid, hydrochloric acid, ethylene cyanide, jetanolamine,
Amines such as triethanolamine, potash alum, ammonium alum, water-soluble aluminium salts such as aluminum sulfate and aluminum chloride, methanol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polyoxyethylene glycol, acetone It contains organic compounds such as KI, NaI, and other iodine compounds as necessary.

Further, during the above process, the second exposure does not necessarily have to be by light. For example, instead of capri with light, it is also possible to decaprate with a capra containing a strong capricating agent such as potassium borooctide, sodium sulfide, or stannous chloride. Furthermore, this step can be omitted by using a fogging developer containing a caplacing agent such as hydrazine as the second developing solution.

The thickness of the emulsion layer of the Lippmann type silver halide photographic light-sensitive material in the present invention is generally about 3 to 8 microns, and the average size of the silver halide grains is generally smaller than 80 nm.

and the ratio of silver halide to hydrophilic colloid binder in the emulsion is preferably at least 1:2 and at most 411
It is. This Lippmann silver octaride emulsion can be produced according to the method described in the following literature.

For example, “Photographic +” by B Graphkid.
Mies Dolly, Vol. 1 (1958), pp. 365-368; Mies and James, The Theory of the Photographic Process (1966), No. 36
Page and National Physical Laboratory's [Notes of Applied Science JA20: r Small-Scale Science of Fine Science.
Grain (Colloidal) Photographic Society Emulsion” P H Clawboard Four Don 196
There is a year 0. Furthermore, UK Patent Application No. 1594877
It can also be made by the method described in No. 0.

Lippmann-type silver halide emulsions with very fine grains can be prepared in the presence of heterocyclic mercapto compounds as described in British Patent No. 1,204,623 or in British Patent Application No. 53025/ No. 69 and No. 5453
It is obtained by precipitation of silver halide in the presence of compounds such as those described in 9/69.

The hydrophilic colloid used as a vehicle for the silver halide may be any of the usual hydrophilic colloids used in photographic light-sensitive emulsions, such as gelatin, albumin, zein, casein, alginic acid, carboxymethyl cellulose, polyvinyl acetate, etc. Coal and poly-N-vinylpyrrolidone can be mentioned.

The silver halide composition of the silver halide emulsion in the present invention includes, for example, 1 chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide, cyclic silver bromide, etc., and has an average grain size of 80 nm. most preferably silver iodobromide containing at most 8 mol % silver iodide.Tubmann type silver halide emulsions can be coated on a variety of supports. Including cellulose ester film, polyvinyl acetal film, polystyrene film, polyethylene terephthalate film, and paper or glass. In producing high-resolution plate materials for the production of masks used in the electronics industry, glass supports are most advantageous due to their high dimensional stability. It can be chemically or optically sensitized. For optical sensitization, any known spectral sensitizers can be used, such as cyanine and merocyanine dyes. Silver halide emulsions for electronic masks according to the invention are sensitized for the green region of the spectrum. most advantageously sensitized. As the exposure light source, it is preferable to select a light source that emits light at a spectrally sensitized wavelength.

The above-mentioned Lippmann type helogonide emulsion can be chemically sensitized by ripening in the presence of a small amount of a sulfur-containing compound such as aryl thiocyanate, aryl thiourea, sodium thiosulfate, etc.

For example, French Patent No. 1,146,955 F! Am, the present tin compounds described in Belgian Patent No. 568,687, the imino-aminomethane'sulfinic acid compounds described in British Patent No. 789,823 and small amounts of noble metal compounds such as gold, platinum. Sensitization can also be achieved by reducing agents such as , palladium, iridium, ruthenium and rhodium.

Furthermore, the secondary emulsion may also contain a compound that sensitizes the emulsion by accelerating development. Such compounds include, for example, U.S. Pat.
990 Specification, British Patent No. 920°637, No. 94
″0.051, 945,340, 991.6
Polyoxyalkylene compounds, such as alkylene oxide condensation products, and quaternary ammonium, quaternary phosphonium and tertiary sulfonium compounds, as described in British Patent No. 08 and Pehegy Patent No. 648.710, as well as Examples include the amino-bioxide onium conductor described in US Pat. No. 1,121,696.

The above emulsion also contains stabilizers such as benzothiazoline-2-
It may also contain compounds such as thione and heterocyclic nitrogen-containing thioxo compounds such as 1-phenyl-2-tetrazoline-5-thousone and hydroxytriazolopyridine. Furthermore, Belgian patents nos. 524,121 and 677
．． 337, GB 1,173,609 and US Pat. No. 3,179,520.

The emulsion layer may also contain a photosensitive dye selected to absorb light at the wavelength at which the photosensitive material was exposed to reduce scattering and reflection of light within the photosensitive material. Details of these dyes can be found in Belgian Patent No. 699,375.
Reference may be made to British Patent Application No. 58844/68, etc. These dyes have a density of 0.605 to 0.20, measured in the spectral band of the exposure light source, for a 1 micron emulsion layer thickness.
It is preferable to use an amount such that a density of 0 is obtained.
Furthermore, for older emulsions, hydrophilic cosidic hardeners such as chromium, aluminum and zirconium salts, formaldehyde, dialdehydes, and tetraxaldehydes,
acrolein, glyoxal, halogen-substituted aldehydic acids such as mucochloric acid and mucobromic acid, diketones such as divinyl ketone, compounds with one or more vinylsulfonyl groups such as divinylsulfone,
1°3.5-Trivinylsulfonylbenzene, vinylcarbonyl, hexahydro-5-) liazine having a genoacetyl and/or baryl group, for example 1,3.
5-Triacrylyl-hexahydro-1,3,5-1
Riazine, 1,3-diacryloyl-5-acetylhexahydro-1,3°5-triazine, 1,3. ! S-)
It is also possible to use additions such as 11acetylhexahydro-1,3,5-)riazine.

British Patent No. 115467 for promoting adhesion of emulsions to glass supports in the production of high resolution cuprate materials.
The silicon compound described in the specification of No. 8/68 can be added to the emulsion, but it is also possible to add all kinds of Ti additives such as a preservative and a coating aid as necessary. .

Example 1 A silver iodobromide emulsion containing 3 moles of silver iodide (
A gelatin concentration of 9%) was prepared. Precipitation conditions were regulated to obtain a Lippmann emulsion with an average grain size of 60 nm.

The above emulsion contains silver hepgenide 1009.
Spectrally sensitized by adding 250 μm of dye.

This resulted in a strong spectral sensitization of this emulsion in the 500-550 nm band. The sensitized emulsion was coated on a glass plate so that the film thickness after drying was 5 μm. The silver device at this time was q20q/1m'.

Each of the thus prepared samples was uniformly exposed to 7 wP. After exposure, the following processing steps 1i! The inversion process was carried out according to the following.

(Salt processing 1il) 1st stage * 20℃ 5 minutes 2) Washing with water 18-21'C 2 minutes 3) Bleaching 18-21'C 2 minutes 4) Washing with water 1
8-21℃ 2 minutes 5) Cleaning 20℃ 5 minutes 6) Water washing 18-21℃ 2 minutes 7) 2nd iI light full exposure 8) Second development 20℃ 5 minutes 9) Water washing
Dry for 5 minutes at 18-21° C. However, in the above treatment step, the exemplified compounds of the present invention were added to the cleaning bath so as to have the composition shown in Table 1. Each sample was processed using these cleaning baths.

In this example, the number of the cleaning bath and the number of the sample were the same.Table 1 The composition of the processing liquid other than the above is as follows.

(1y4.*Liquid) Hydroquinone 4[1 Anhydrous sodium sulfite 100g Sodium hydroxide 4511 Potassium bromide
Add 40g of water to bring the volume to 11◇ (Bleach solution) Potassium dichromate 209 Concentrated sulfuric acid
15111j Water was added to make 1j.

(Second developer) Hydroquinone 5.9 monomethyl-
p-Aminophe/-Rusulfate II Anhydrous Sodium Sulfite 40Ii Sodium Carbonate
30I Potassium Bromide 0.5# Water was added to 1#.

After the treatment, the deterioration density of each sample was measured using a Sakura PD Mu-65 densitometer (manufactured by Konishiroku Photo Industry).

The results are shown in Table 2.

Table 2 As shown in the results of Table 2, samples (2) to (7) treated with a clean bath containing the exemplified compounds of the present invention (su and (7))
) had higher image density than comparative sample (1).

Example-2 A sample was prepared in the same manner as in Example 1, and this sample was divided into eight equal parts. Each sample was exposed under the same conditions with green monochromatic light.

The exposure was carried out through a test pattern separated by the same spacing as the lines themselves and commonly used for quantitative evaluation of the amount of material to be used in electronic mask formability. These samples were subjected to the same inversion treatment as in Example 1. However, the composition of the cleaning bath was as shown in Table 3.

Table 3) and (11) of the samples treated with the cleaning bath of the present invention have low m1gI concentration after treatment, poor sharpness, and iw
The edges of * are rounded. At the same time, the reproducibility of the line width became poorer and became thinner. However, sample e) according to the invention
, (10), (12) to (15) #i ISUREMO The above-mentioned inconvenient phenomena did not occur, and the image reproducibility was excellent.

Agent Yoshimi Kuwa Hara

Claims (1)

[Claims] In the Lippmann-type reversal processing method for silver oxide photographic light-sensitive materials, sulfite ions following the bleaching bath are added at least 40%.
The solubility product (F
1. A method for processing a Tubmann type silver halide photographic light-sensitive material, which comprises adding at least one organic compound having a lap ) of 1188 or more at 25°C.