JP2002090981A - Processing method for mask material for exposure - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a processing method for a mask material for exposure by which the line width of an image, particularly that of thin lines can be faithfully reproduced independently of a peripheral image. SOLUTION: In the processing method for a mask material for exposure in which a silver halide photosensitive material with a physical developing nucleus layer between a glass substrate and a silver halide emulsion layer is physically developed to form a metal silver image of <=1 μm thickness on the glass substrate and the maximum optical density of the metal silver image is >=1.0, the first step is a developing step comprising at least two developing steps, a first developing solution used in the first developing step contains a sulfite and does not substantially contain a silver halide solvent other than the sulfite and processing is carried out with a developing solution containing both a sulfite and a silver halide solvent other than the sulfite in at least one developing step after the first developing step.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] 1. Field of the Invention [0002] The present invention relates to a method for processing an exposure mask material for forming a circuit pattern or the like.

[0002]

2. Description of the Prior Art According to Isao Tanabe, Yoichi Takebana, and Moruhisa Homoto, "Story of Photomask Technology", Industrial Research Committee (1996), an exposure mask is a silver halide photographic emulsion layer (transparent substrate) such as a film or glass. It is manufactured by providing a thin metal film (hard mask) such as an emulsion mask) or chromium. With the recent trend toward smaller and finer printed circuit boards, exposure masks are required to have higher dimensional accuracy than ever before, and the market for base materials is gradually shifting from film to glass.

When the silver halide photographic photosensitive layer is irradiated with light, the emulsion mask forms a blackened image by developing silver halide in a photosensitive portion. Emulsion masks using silver salt photography are easy to achieve high sensitivity corresponding to a laser light source and the system is simple.
Since the blackened silver is dispersed in a relatively thick film having a thickness of micron to 6 microns, the image quality is deteriorated by the thickness of the image no matter how hard the photographic processing is performed.

On the other hand, the light shielding film of the hard mask is a metal thin film, and the mainstream is a chromium film having a thickness of about 0.1 μm.
Therefore, the reproducibility of a fine image of about 1 micron is excellent, but the steps such as the etching process are complicated, and it has not yet been possible to easily obtain an exposure mask using a hard mask. In addition, the sharpness and stability of the resist film formation and drawing process using a high-sensitivity photopolymer are still insufficient, and are not suitable for directly drawing a fine image with a laser light source or the like. Moreover, chromium has environmental problems, and in recent years it has been required to switch to another method.

[0005] We have already proposed in Japanese Patent Application Laid-Open No. 12-10258 to obtain a light-shielding film for forming a circuit pattern for directly forming a silver image on a transparent substrate. According to this, the obtained exposure mask does not contain gelatin, so that even if it is used continuously as an exposure mask, it is not discolored or denatured by heat or ultraviolet rays like an emulsion mask, and it is not coated on a glass substrate. A metallic silver image having a thickness of 1 micron or less can be formed, and a metallic silver image having a maximum optical density of 1.0 or more can be obtained, so that a fine image can be sharply reproduced. However, there is a problem that the reproducibility of an image, particularly, the reproducibility of the line width of a thin line depends on the surrounding image, and a countermeasure has been required. Further, it has been demanded that the edges of finer images be reproduced sharply.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method of processing an exposure mask material in which an image, particularly a fine line width, is faithfully and sharply reproduced without being affected by a peripheral image. It is in.

[0007]

The present inventors have studied and found that a physical development nucleus layer is provided between a glass substrate and a silver halide emulsion layer, and a physical development nucleus layer having a thickness of 1 μm is formed on the glass substrate by physical development. Forming the following metal silver image, in the method of processing a silver halide photosensitive exposure mask material having a maximum optical density of 1.0 or more of the metal silver image, the first step is a development step,
The developing step comprises at least two developing steps;
The first developer used in the developing step contains a sulfite,
Silver halide solvents other than sulfites are not substantially contained,
In at least one of the developing steps other than the first developing step, the above-mentioned problem has been solved by processing with a developing solution containing both a sulfite and a silver halide solvent other than the sulfite. Preferably, the pH of the first developer is 12.
5 or less, more preferably, the temperature of the first developer is lower than the temperature of the developer corresponding to the other development steps, and more preferably, the first developer contains a polyvalent anion. By doing so, the above problem was solved. More preferably, the above problem has been solved by the silver halide photosensitive exposure mask material containing a layer composed of a metal oxide between the glass substrate and the physical development nucleus layer.

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
The exposure mask material of the present invention is prepared by a silver complex salt diffusion transfer method (hereinafter referred to as D
A silver film is formed on a glass substrate according to the principle of the TR method. The DTR method is described in U.S. Pat. No. 235,2014, or as described in "Photographic Silver Halide Diffusion Processes" by Andre Lott and Edith Weide, published by Focal Press, London, NY (1972). Unexposed silver halide dissolves and is converted into a soluble silver complex compound, which diffuses in the silver halide emulsion layer and is developed at the location of physical development nuclei to form a silver film. On the other hand, the silver halide in the exposed portion has a latent image nucleus formed by light irradiation, and is chemically developed in the emulsion layer. If this is washed with warm water after development, the silver halide photographic photosensitive layer containing water-soluble gelatin as the main binder is removed, leaving only the silver film formed on the physical development nuclei in the unexposed areas on the glass substrate. To form an image. This makes it possible to obtain a metallic silver thin film having a thickness of 1 micron or less without containing water-soluble gelatin, and having a maximum optical density of 1.0.
Since the above metal silver image is obtained, even a fine image can be sharply reproduced.

As the glass substrate of the present invention, a glass substrate known to those skilled in the art can be used. It is necessary to select according to the application, required performance, etc.
Soda lime glass such as soda lime and white crown; low expansion glass such as borosilicate, alkali-free, and aluminosilicate; and synthetic quartz glass.

The physical development nucleus of the physical development nucleus layer used in the present invention may be a known physical development nucleus usually used in a silver complex salt diffusion transfer method, for example, a metal colloid such as gold or silver or a silver or palladium or zinc colloid. A metal sulfide obtained by mixing a water-soluble salt and a sulfide can be used. Various hydrophilic colloids can be used as the protective colloid. For details and production method thereof, for example, JP-B-48-30562,
JP-A-48-55402 and JP-A-53-21602, Focal Press, London New York (1
972) Published by Andre Lott and Edith Weide "Photographic Silver Halide Diffusion Processes". Further, a surfactant can be contained as a coating aid.

In the present invention, various types of silver halide emulsions known to those skilled in the art can be used according to the required sensitivity, photographic characteristics, and combination with processing agents. Used are silver chloride, silver chlorobromide, silver chloroiodide, and silver chloroiodobromide. Among them, silver chloride having a halogen composition of 70 mol% or more is particularly preferable.
The average grain size of the silver halide crystals is 0.05 to 0.5 μm.
It is. The crystal habit of the silver halide crystal may be any of a regular hexahedron, a regular octahedron, a regular hexahedron, and a tabular shape, but a regular hexahedron is preferred. It can also have a core-shell structure. When forming a silver halide crystal, an iridium compound and a rhodium compound may be contained. The contents of the iridium compound and the rhodium compound differ depending on the desired sensitivity and the performance to be imparted, but are preferably 10 ^-8 to 10 ^-3 mol per mol of silver halide. In addition, the silver halide emulsion of the present invention can be further subjected to chemical sensitization such as reduction sensitization, sulfur sensitization, gold sensitization, and gold-sulfur sensitization as needed, thereby obtaining higher sensitivity.

The silver halide emulsion of the present invention may be an argon laser, a helium / neon laser, a semiconductor laser,
If necessary, spectral sensitization can be carried out with a sensitizing dye used in a usual silver halide photographic emulsion for the purpose of supporting various light sources such as a light emitting diode. It is necessary to select according to the wavelength and intensity of the light source, the kind of the compound to be added, but any dye such as cyanine dye, merocyanine dye, rhodocyanine dye, oxonol dye, styryl dye, base styryl dye is added alone or in combination be able to. Dyes and pigments used in ordinary silver halide photographic emulsions can be added in order to cope with image deterioration due to irradiation or halation.

If necessary, the following additives known to those skilled in the art can be added to the emulsion layer of the present invention. Anionic, cationic, betaine, nonionic surfactants, thickeners such as carboxymethyl cellulose, coating aids such as antifoaming agents, chelating agents such as ethylenediaminetetraacetate, hydroquinones, polyhydroxybenzenes, 3-pyrazolidinones May be contained. Further, stabilizers such as azaindenes and heterocyclic mercapto compounds, and fogging inhibitors can also be added.

As the binder for the silver halide emulsion layer of the present invention, water-soluble gelatin alone or in combination with casein, dextrin, gum arabic, polyvinyl alcohol, starch and the like can be used. As the water-soluble gelatin, any of acid-treated gelatin, alkali-treated gelatin, gelatin derivatives, grafted gelatin, low molecular weight gelatin and the like can be used. In the present invention, a hardening agent known to those skilled in the art may be added to harden the silver halide emulsion layer.

The thickness of the metallic silver image of the exposure mask of the present invention is 1 micron or less, and the maximum optical density of the metallic silver image is 1.0 or more. The surface of the glass substrate is not always flat, and the thickness of the metallic silver film is not always constant due to the influence of the deviation in the coating process or the particulate matter contained in the mask material for exposure. Therefore, the thickness of the metallic silver image in the present invention is shown as an average thickness in a size of 10 mm × 10 mm square or more. The optical density of the metallic silver image varies depending on the type of the image. For example, in a very fine image, the optical density can be reduced to half or less than that in a large area (so-called solid part). Similarly, in the present invention, the maximum optical density refers to the maximum density at the central portion of a metallic silver image of 10 mm × 10 mm square or more.

In the exposure mask material of the present invention, an intermediate layer comprising a hydrophilic colloid may be provided between the physical development nucleus layer and the physical development nucleus layer, if necessary, in addition to the silver halide emulsion layer and the physical development nucleus layer. Further, an uppermost layer may be provided as a protective layer.
A dye or pigment known to those skilled in the art may be added to the above-mentioned physical development nucleus layer or intermediate layer for the purpose of preventing light reflection and scattering on the glass surface, that is, image deterioration due to halation. For the purpose of preventing reflection and scattering of light on the back surface of the glass, that is, image deterioration due to halation, a dye or pigment known to those skilled in the art is contained on the surface (back surface) opposite to the silver halide emulsion layer with respect to the glass substrate. A hydrophilic colloid layer may be provided.

In the processing step of the exposure mask material of the present invention, the first step is a developing step. In the present invention,
The development step comprises at least two development steps. In the developing step of the present invention, the latent image nucleus formed by light irradiation with silver halide in the exposed part is chemically developed, and the silver halide in the unexposed part is dissolved by a silver halide solvent to form a soluble silver complex compound. This is a step of diffusing in the silver halide emulsion layer and developing at the location of the physical development nucleus to form a silver film (physical development). Focal Press, London New York (1972) Published by Andre Lott and Edith Weide "Photographic Silver Halide Diffusion Processes" describes various applications of the DTR method, all of which are halogenated. The above chemical development and physical development are simultaneously advanced by performing development processing in an alkaline developer containing a silver solvent. In a typical copying system as an application example of the DTR method, a positive sheet coated with a silver halide emulsion and an image receiving sheet (negative sheet) coated with a physical development nucleus are overlapped so that the sheet is overlapped once. However, it is difficult to impregnate another processing solution into the solution, and compounds having various functions have been coexisted in one processing solution. Also, in an offset printing plate, which is a typical example of a mono-sheet type, there is no disclosure of a technique of dividing a developing process into a plurality of processes. As a result of intensive studies, we have divided the developing step into two steps, the only silver halide solvent contained in the first developing solution used in the first developing step is only sulfite, and the second developing step is used in the second developing step. (2) It has been found that the reproducibility of an image, in particular, the line width of a fine line is improved by incorporating a sulfite and another silver halide solvent in combination in the developer. Even if only a sulfite is contained as a silver halide solvent, a silver image cannot be formed by the DTR method, and the processing method of the present invention allows only the chemical development to proceed in the first development step, and mainly comprises the second development step. Since physical development is proceeding, it can be said that this is a new DTR development method in which chemical development and physical development are completely separated from the conventional DTR technology.

In the present invention, the sulfite is added mainly as a preservative, not as a silver halide solvent. Examples of the sulfite include sodium sulfite and potassium sulfite. In order to fulfill the function as a preservative, the amount of sulfite added to the first developer and the second developer may be the same or different.
10 g or more per L, preferably 20 g to 150 g.

In the present invention, examples of the silver halide solvent other than the sulfite include various solvents known to those skilled in the art as having a capability of dissolving silver halide. Examples thereof include thiosulfates, amines, thioethers, and thiocyanates. Examples of the thiosulfate include sodium thiosulfate, potassium thiosulfate, and ammonium thiosulfate. The amount of the thiosulfate added to the second developer can take various values depending on the type (composition or size) of the silver halide emulsion, the combination with the composition of the developer, and the like. 0.1 g or more, preferably 0.5 g to 50 g per 1 L of the developer is good. Amines are compounds in which ammonia is a substituted or unsubstituted saturated or unsaturated alkyl group, cycloalkyl group,
It is substituted by an alkoxy group, an aryl group, an alkanoyl group, an aroyl group, or a heterocyclic group, and these substituents may combine with each other to form a ring. Specific examples are shown below.

[0020]

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[0021]

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[0022]

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[0023]

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[0024]

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[0025]

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[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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The amount of the amines to be added to the second developer can take various values depending on the type (composition or size) of the silver halide emulsion and the combination with the composition of the developer. Developer 1
1 g to 50 g per L is good. In the present invention, the second
The silver halide solvents other than the sulfite contained in the developer may be used alone or in combination.

In the present invention, the first developer contains substantially no silver halide solvent other than sulfite. The term "substantially not contained" means that the silver halide photosensitive exposure mask material of the present invention is immersed in a single solution having a concentration in a developer and contains no component in which 5% or more of the silver halide is dissolved. means.

In the present invention, the first development step corresponding to the chemical development and the second development step mainly corresponding to the physical development can be further divided into a plurality of steps. In this case, the requirements for the second developing step and the second developing solution may be satisfied in at least one of the developing steps other than the first developing step.

In the developer of the present invention, in addition to the above components,
Developing agents (eg, polyhydroxybenzenes, 3-pyrazolidinones), alkaline substances (eg, potassium hydroxide, sodium hydroxide), thickeners (eg, carboxymethylcellulose), antifoggants (eg, potassium bromide), development modifiers (For example, a polyoxyalkylene compound) and the like.

In the present invention, the pH of the developer can take various values known to those skilled in the art, but is usually 10 to 14, preferably 11 to 14. As a preferred embodiment of the present invention,
The pH of the first developer is preferably 12.5 or less. More preferably, it is 10.8 to 12.5.

Further, in a preferred embodiment of the present invention, the first
The temperature of the developing solution is equal to or lower than the minimum temperature of the developing solution corresponding to the other developing steps. However, the temperature accuracy that can be substantially controlled by the structure of the developing tank, the processing environment, the stirring conditions, the type of the temperature sensor, the heating / cooling method, etc. is ± 0.0 to ± 2.
Since a wide range of values can be taken up to 0 ° C. (even if the same temperature is set, a difference of about 2 ° C. may occur due to fluctuations in long-term observation). A difference of about ° C is also included.

Further, as a more preferred embodiment of the present invention,
The first developer contains a polyvalent anion. It is known to those skilled in the art that a photographic developer contains a polyvalent anion as a component having various functions. In the present invention, an additive which gives a polyvalent anion by dissolving such as sulfite and polyhydroxybenzenes has already been exemplified, but the polyvalent anion in the present invention means a function as a preservative or a developing agent. And specific examples of those that give the polyvalent anion of the present invention include phosphate, sulfate, carbonate, borate and the like. The addition amount is preferably from 0.01 to 2 mol, more preferably from 0.05 to 1 mol, per liter of the developer.

As described in the specification of Japanese Patent Application No. 11-340439, it is preferable to treat the mask material for exposure in a step such as fixing and washing with water after the development step. Fixation,
The washing step can also consist of multiple steps. The fixing step here is different from the fixing step of a general black-and-white silver halide photographic material. Hereinafter, the fixing process will be described.

In the fixing step of the present invention, the silver halide emulsion layer is removed, and the non-image portion exposes the glass substrate surface,
The image area is a step of exposing the metallic silver image. The pH of the fixing solution is preferably 5 or more, more preferably 5.5 or more and 8 or more.
The following is good. The fixer preferably contains a pH buffer component. As the pH buffer component, various substances known to those skilled in the art can be used. Specific examples thereof include potassium hydrogen phthalate + hydrochloric acid, potassium hydrogen phthalate + sodium hydroxide, dipotassium hydrogen phosphate + 1 potassium hydroxide + hydroxide. Combinations of sodium and the like. Further, an antiseptic can be contained for the purpose of preventing spoilage of the removed gelatin.

The fixer of the present invention may contain a protease. As proteolytic enzymes,
Any vegetable or animal enzyme capable of degrading proteins such as gelatin, known to those skilled in the art, can be used. Examples include pepsin, rennin, trypsin, chymotrypsin, cathepsin, papain, ficin, thrombin, renin, collagenase, bromelain, bacterial proteinase, and the like. Among these, trypsin, papain, ficin, and bacterial proteinase are particularly preferred. The amount of proteolytic enzyme added to the fixing solution cannot be specified unconditionally because the enzyme activity varies depending on the temperature and other additives, but the enzyme activity is 10% per liter.
It is preferable to add so as to be not less than 00 PUN and not more than 1,000,000 PUN. Here, the enzyme activity is defined as 5% of 0.6% milk casein (pH 7.5, M / 25 phosphate buffer).
The activity of releasing 1 g of folin color corresponding to 1 μg of tyrosine per minute as a TCA soluble component per minute when 1 g of an enzyme is added to 1 and reacted at 30 ° C. for 10 minutes is defined as 1 PUN.

The fixing solution may contain a phosphate. Phosphates include phosphoric acid, disodium monohydrogen phosphate, monosodium dihydrogen phosphate, monohydrogen phosphate
Potassium or the like can be used. In addition, 30
The temperature is preferably maintained at a temperature of at least 32 ° C, more preferably at least 32 ° C and at most 45 ° C.

The water washing step in the present invention is the same as the water washing step of a general black-and-white silver halide photographic light-sensitive material, in which substances remaining on the surface in the previous processing steps are washed away, and unevenness occurs after drying. It is another object of the present invention to prevent the remaining substances from deteriorating the image due to aging or oxidation by air. Preferably, it is good to wash with pure water.

The exposure mask material of the present invention can be processed manually. However, it is possible to perform the deflection for each treatment, the deflection due to the aging due to the fatigue of the processing solution, and the like, and the deflection depending on the location in one exposure mask material. For the purpose of reducing as much as possible, it is preferable to carry out processing with an automatic developing machine as described in Japanese Patent Application No. 11-340440.

As a preferred embodiment of the present invention, it is preferable to include a layer composed of a metal oxide between the glass substrate and the physical development nucleus layer of the silver halide photosensitive exposure mask material. The metal oxide of the present invention refers to, for example, a metal oxide such as colloidal silica, colloidal alumina, titanium oxide, zinc oxide, zirconium oxide, or a hydroxide thereof. Colloidal silica is a colloidal substance of amorphous silicic anhydride. In addition to unmodified, the surface of silica is modified with ions and compounds such as ammonia, calcium, and alumina to behave in response to ionicity and pH fluctuation of particles. Modified colloidal silica in which is changed is also included. Colloidal alumina is an amorphous or pseudo-boehmite (including boehmite in a broad sense) alumina hydrate in the form of a colloid having a dispersed shape such as a feather-like, fibrous, or plate-like shape. Further, saponite, hectorite, smectite group such as montmorillonite, vermiculite group, kaolinite-serpentine group such as kaolinite and halosite, natural clay minerals such as sepiolite, such as fluorophlogopite, fluorine tetrasilicic mica, teniolite and the like Synthetic inorganic polymers such as fluoromica and synthetic smectite can also be used.

The layer composed of these metal oxides or hydroxides can be prepared by any method known to those skilled in the art, but is most easily finely dispersed in a solvent and formed on a transparent substrate. Coated and held. In this case, the particle diameter of the finely dispersed metal oxide or hydroxide is about 1 nm to 100 μm. After being applied on a transparent substrate and dried, the metal oxide particles may be heated to 150 ° C. or higher in order to increase the bonding force between the particles. Since heating to 600 ° C. or more causes particle growth of the metal oxide, it is preferable that the heating be performed at 150 ° C.
It is preferable to heat at a temperature of not less than 500C and not less than 500C.

[0048]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but it should not be construed that the invention is limited thereto without departing from the spirit of the present invention.

Example 1 A titania sol TA-15 manufactured by Nissan Chemical Industries, Ltd. was applied to a soda-lime glass substrate to a thickness of 0.3 μm, dried at room temperature, and heated at 200 ° C. for 30 minutes. .

A palladium sulfide physical development nucleus solution is prepared in an aqueous solution of polyethylene glycol / alkyl ether, and is applied onto the above-mentioned colloidal silica-coated soda-lime glass substrate so that the amount of palladium sulfide nuclei is 1.0 mg / m ^2. And dried.

A silver halide emulsion was prepared by the following method. Silver chlorobromide of 15 mol% of silver bromide doped with potassium hexachloroiridate (IV) having an average particle size of 0.25 μm and having an average particle diameter of 0.25 μm per mol of silver by a control double jet method using alkali-treated gelatin. After preparing the emulsion, the surface of the silver chlorobromide emulsion was converted to silver iodide by adding a potassium iodide solution, and the emulsion was desalted by flocculation. Further, this emulsion was subjected to gold / sulfur sensitization, and a sensitizing dye was added thereto for spectral sensitization. Further, 10 ^-3 mol of 1-phenyl-5-mercaptotetrazole was added to this silver halide emulsion per mol of silver halide. The silver halide emulsion thus prepared is
The final preparation was performed so that the gelatin was 0.7 g per 1.0 g of silver halide, and the coating amount of silver halide was 6 g / m ^2.
Was applied to the glass substrate coated with the physical development nucleus layer and dried to prepare an exposure mask material sample (A).

A flat laser plotter FR manufactured by Dainippon Screen Mfg. Co., Ltd.
After scanning and exposing a 20-micron line-and-space image (1000 lines + 1000 spaces) by changing the laser power under the conditions of a drawing pitch of 1 micron and a beam diameter of 5 microns using -8000, Table 1 and After being immersed in the first developer shown in Table 2 while being rocked for 1 minute, it was immersed in the second developer shown in Table 1 while being rocked for 1 minute. Then, in a disodium monohydrogen phosphate + phosphate buffer containing sulfite and defoamer, Nagase & Co., Ltd.
30 g (a kind of bacterial proteinase) manufactured by Dip Transfer Co., Ltd. in a diffusion transfer fixing solution at 35 ° C. to which 3 g was added per liter of fixing solution for 1 minute, and then the fixing solution was applied to the surface of the mask material for exposure with a shower nozzle, and halogenated. After removing the silver emulsion and finally washing with pure water, samples A to P were obtained by removing water with an air gun.

The laser power at which the line width at the center of the line-and-space images of the samples A to P was 20 μm was used as standard exposure, and the sharpness (edge sharpness) of the line edge was evaluated according to the following criteria. ×: Very blurred. Not practical. Δ: Blurred, but practically acceptable. ：: Sharp. A: Very sharp. At this time, the line width at the end was measured. Table 1 and Table 2
Shows the results.

[0054]

[Table 1]

[0055]

[Table 2]

[0056]

As described above, according to the processing method of the present invention, an image can be obtained without being affected by peripheral images.
In particular, an exposure mask material in which the fine line width was faithfully reproduced was obtained. Further, according to a preferred embodiment of the present invention, it was possible to obtain an exposure mask material which gives an image having excellent edge sharpness.

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[Procedure amendment]

[Submission date] October 11, 2001 (2001.10.
11)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0054

[Correction method] Change

[Correction contents]

[0054]

[Table 1]

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0055

[Correction method] Change

[Correction contents]

[0055]

[Table 2]

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Toshihiko Neko 3-4-2 Marunouchi, Chiyoda-ku, Tokyo F-term in Mitsubishi Paper Mills Co., Ltd. (Reference) 2H095 BB38 BC08 BC11 BC27

Claims (5)

[Claims] 1. A physical silver halide emulsion layer having a physical development nucleus layer between a glass substrate and a silver halide emulsion layer, wherein a metallic silver image having a thickness of 1 μm or less is formed on the glass substrate by physical development. In the method for processing a silver halide photosensitive exposure mask material having a maximum optical density of 1.0 or more, the first step is a developing step, and the developing step comprises at least two developing steps. The first developer used contains a sulfite, contains substantially no silver halide solvent other than the sulfite, and contains at least one of the developing steps other than the first developing step.
A method for treating an exposure mask material, wherein the method comprises treating with a developer containing both a sulfite and a silver halide solvent other than the sulfite. 2. The method according to claim 1, wherein the pH of the first developer is 12.5 or less. 3. The method according to claim 1, wherein the temperature of the first developing solution is equal to or lower than the minimum temperature of the developing solution corresponding to the other developing steps. . 4. The method according to claim 1, wherein the first developer contains a polyvalent anion. 5. A silver halide photosensitive exposure mask material comprising a layer composed of a metal oxide between a glass substrate and a physical development nucleus layer. Or the method for treating a mask material for exposure according to item 4.