JP2003315957A - Mask material for exposure - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a mask material for exposure excellent in reproducibility of a fine image and capable of easily manufacturing a mask for exposure. <P>SOLUTION: In the mask material for exposure having at least a silver halide emulsion layer on a glass substrate, a relief image is formed by tanning development, the thickness of the silver halide emulsion layer is 0.5-5 μm and the maximum density of the image portion is ≥3. Preferably a low molecular weight gelatin or/and a tanning developer are contained in the silver halide emulsion layer or the like, ≥5×10<SP>-3</SP>mol/m<SP>2</SP>silver halide emulsion grains are contained and thickness corresponding to 5×10<SP>-3</SP>mol/m<SP>2</SP>of the grains is ≤2 μm, the sensitivity of the lower layer of the silver halide emulsion layer is higher than that of the upper layer, a metal oxide layer is included, or a silver halide emulsion is removed by a process not including contact. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an exposure mask material for forming a circuit pattern.

[0002]

2. Description of the Prior Art According to Isao Tanabe, Yoichi Takebana, and Morishisa Homoto, "Photomask Technology", Industrial Research Group (1996), an exposure mask is a thin film of metal such as chrome (hard) on a transparent substrate such as film or glass. Mask) or a silver halide photographic emulsion (emulsion mask).

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, 1
Although it is excellent in reproducibility of a fine image of about μm, it is not possible to easily obtain an exposure mask with a hard mask because of complicated processes such as etching treatment. Moreover, the sharpness and stability of the resist film formation and drawing process using a high-sensitivity photopolymer are still insufficient, and it is not suitable for drawing a fine image directly with a laser light source. Moreover, chromium has environmental problems, and in recent years, it has been urged to switch to another method.

On the other hand, in the emulsion mask, when the silver halide photographic photosensitive layer is irradiated with light, the silver halide in the photosensitive portion forms a blackened image by the development processing. Emulsion masks using silver salt photography are easy to increase the sensitivity corresponding to the laser light source, and the system is simple. However, gelatin, which is the binder of the silver halide emulsion, remains in the non-image area, and this causes deterioration such as yellowing due to repeated UV irradiation and temperature changes during photoresist exposure, resulting in deterioration of image quality. It's a problem.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide an exposure mask material which is excellent in reproducibility of a fine image and which allows an exposure mask to be easily prepared.

[0006]

DISCLOSURE OF THE INVENTION As a result of investigations by the present inventors, in a mask material for exposure having at least a silver halide emulsion layer on a glass substrate, a relief image was formed by curing and developing treatment, and halogenation was performed. The silver emulsion layer thickness is 0.5 μm or more and 5 μm or less, and the maximum density in the image area is 3 μm.
The above problem can be solved by the exposure mask material having the above characteristics. The average molecular weight of the silver halide emulsion layer and / or the hydrophilic colloid layer containing a hydrophilic polymer as a binder is 5
The above problem could be solved by a mask material for exposure which is characterized by containing less than 10,000 low molecular weight gelatin. Also, the silver halide emulsion layer is 5 × 1 per 1 m ^2.
The thickness of the silver halide emulsion layer containing 0 to 3 mol or more of silver halide emulsion grains and corresponding to 5 × 10 −3 mol of silver halide grains per 1 m ^{2 from the} glass substrate is 2 μm or less. The above-mentioned problem could be solved by the exposure mask material which is characterized in that it is present. Further, the above problem can be solved by the exposure mask material which is characterized in that the sensitivity of the lower layer is higher than that of the upper layer of the silver halide emulsion layer, starting from the glass substrate. Also,
The above problem could be solved by an exposure mask material characterized by containing a layer composed of a metal oxide between a glass substrate and a silver halide emulsion layer. Further, the above problems can be solved by an exposure mask material characterized by containing a curing developer in a silver halide emulsion layer and / or a hydrophilic colloid layer containing a hydrophilic polymer as a binder. did it. Further, the above problem could be solved by an exposure mask material which is characterized in that the silver halide emulsion in the unexposed portion is removed in a step that does not substantially involve physical contact with a peeling roller or the like.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below.
The present invention forms a relief image on a glass substrate by the principle of the curing and developing method. Curing and developing method is J. Photo. Sc
i. Magazine No. 11, p 1, by AG Tull (1963) or "The T
heory of the photographic Process (4th edition, p
326-327) ", TH James et al., A non-hardened silver halide emulsion layer substantially free of a hardener prepared on a substrate is formed into a polyhydroxybenzene-based emulsion layer. By treating with a developing solution containing a developing agent,
When the developing agent reduces the exposed silver halide, gelatin is crosslinked with an oxide compound generated from the developing agent itself to form an image-wise hardened film. Since the silver halide in the unexposed area is not reduced by the developing agent, no oxidation compound of the developing agent is produced and the gelatin hardening reaction does not occur. When this is washed with warm water after development, the silver halide photographic photosensitive layer in the unexposed area containing water-soluble gelatin as a main binder is removed, and only the image area crosslinked in the exposed area remains on the glass substrate. Form a relief image. This does not contain water-soluble gelatin in the non-image area,
Moreover, an image in which the film thickness of the silver halide emulsion layer is 0.5 μm or more and 5 μm or less and the maximum density of the image area is 3 or more can be obtained. The present inventors have performed exposure for printing a pattern of an electronic circuit. I found that it can be used as a mask.

As the glass substrate according to the present invention, glass substrates known to those skilled in the art can be used. Application,
Although it needs to be selected depending on the required performance and the like, examples thereof include soda lime glass such as soda lime and white crown, low expansion glass such as borosilicate, alkali-free, aluminosilicate, and synthetic quartz glass.

The silver halide emulsion can be prepared by any method known to those skilled in the art, but the double jet method is the most preferable method for efficiently preparing the silver halide having the composition of the present invention. In the double jet method, a solution containing silver ions and a solution containing halogen ions are injected into a gelatin solution while controlling the injection amount to grow silver halide grains and prepare a silver halide emulsion. . The composition of silver halide can be easily changed by changing the kind and ratio of halogen in the solution containing halogen ions.

The average grain size of the silver halide crystals is 0.1.
It is 5 to 0.5 μm, preferably 0.2 to 0.4 μm. The crystal habit of the silver halide crystal may be any of a regular hexahedron, a regular octahedron, a regular hexahedron, a tabular shape and the like, but a regular hexahedron is preferred. It can also have a core-shell structure. Further, an iridium compound and a rhodium compound may be contained when forming a silver halide crystal. The content of the iridium compound and the rhodium compound varies depending on the desired sensitivity and the performance to be imparted, but 10 ^-8 to 1 per mol of silver halide
0 ^-3 mol are preferred. Moreover, the silver halide emulsion according to the present invention can be subjected to reduction sensitization, sulfur sensitization, gold sensitization,
Higher sensitivity can be obtained by chemical sensitization such as gold sulfur sensitization.

Examples of the water-soluble iridium salt used in the present invention include iridium chloride, ammonium hexachloroiridate, potassium hexachloroiridate and the like. The amount of these water-soluble iridium compounds added is preferably 5.0 × 10 ⁻⁸ mol or more, and more preferably 1 × 10 ⁻⁷ to 1 × 10 ⁻⁵ mol, per mol of silver halide. The water-soluble iridium salt can be added at any time during the silver halide emulsion preparation process.
It is preferably added during the formation of silver halide grains.

Examples of the water-soluble rhodium salt used in the present invention include rhodium monochloride, rhodium dichloride, rhodium trichloride and ammonium hexachlororhodate, but water-soluble trivalent rhodium compounds are preferable. The amount of these water-soluble rhodium compounds added is preferably 5.0 × 10 ⁻⁹ mol or more, and more preferably 2 × 10 ⁻⁸ to 1 × 10 ⁻⁶ mol, per mol of silver halide. The water-soluble rhodium salt can be added at any timing in the step of preparing a silver halide emulsion, but is preferably added during the formation of silver halide grains.

In the exposure mask material of the present invention, in addition to the silver halide emulsion layer, an intermediate layer made of a hydrophilic colloid may be provided between the glass material and the glass substrate, if necessary. That is, it may be provided as a protective layer. Further, it may be provided as a hydrophilic colloid layer opposite to the silver halide emulsion layer, that is, as a backing layer.

The exposure mask material of the present invention may be added with dyes and pigments used in ordinary silver halide photographic emulsions in order to cope with image deterioration due to irradiation or halation. As the dye and pigment contained in the hydrophilic colloid layer and the silver halide emulsion layer used in the present invention, those known to those skilled in the art can be used alone or in combination. Since the terms dye and pigment have unique definitions for each industry used, there is no general standard to distinguish them clearly, but a dye is a colorant that dissolves uniformly in water, and a pigment is It is easy to understand when it is distinguished as a colorant that is hardly dissolved in water and forms particles in water. The dye preferably contains a plurality of water-soluble groups such as a sulfonic acid group or a carboxylic acid group in the molecule in order to enhance the solubility in water.

The dye used in the present invention can be selected from various kinds, but it must be selected according to the spectral sensitivity wavelength of the silver halide emulsion. Typical examples of dyes are shown below.

[0016]

[Chemical 1]

[0017]

[Chemical 2]

[0018]

[Chemical 3]

[0019]

[Chemical 4]

[0020]

[Chemical 5]

The pigment used in the present invention can be selected from various types, but it must be selected according to the spectral sensitivity wavelength of the silver halide emulsion. Typical examples of pigments are shown below.

[0022]

[Chemical 6]

[0023]

[Chemical 7]

[0024]

[Chemical 8]

[0025]

[Chemical 9]

[0026]

[Chemical 10]

[0027]

[Chemical 11]

[0028]

[Chemical 12]

[0029]

[Chemical 13]

[0030]

[Chemical 14]

[0031]

[Chemical 15]

[0032]

[Chemical 16]

[0033]

[Chemical 17]

[0034]

[Chemical 18]

[0035]

[Chemical 19]

The silver halide emulsion according to the present invention is used in an ordinary silver halide photographic emulsion as necessary for the purpose of adapting to various light sources such as an argon laser, a helium / neon laser, a semiconductor laser and a light emitting diode. Spectral sensitization can be performed by the sensitizing dye. It is necessary to select it depending on the wavelength and intensity of the light source and the type of compound to be added, but it is necessary to add all dyes such as cyanine dyes, merocyanine dyes, rhodacyanine dyes, oxonol dyes, styryl dyes, and base styryl dyes individually or in a mixture. be able to. Examples of sensitizing dyes are shown below.

[0037]

[Chemical 20]

[0038]

[Chemical 21]

[0039]

[Chemical formula 22]

[0040]

[Chemical formula 23]

[0041]

[Chemical formula 24]

[0042]

[Chemical 25]

[0043]

[Chemical formula 26]

[0044]

[Chemical 27]

These sensitizing dyes may be used alone or in combination of two or more kinds. The amount of the sensitizing dye to be used cannot be unconditionally specified depending on the characteristics of the silver halide emulsion and the intensity of the target light source, but it is 1 × 10 ⁻⁷ to 1 × 10 ⁻² mol per mol of silver halide, particularly 1 mol. × 10 ^-6 to 1 × 1
It is preferably 0 ^-3 mol. The time of addition may be any time before the silver halide emulsion is coated.

If necessary, the following additives known to those skilled in the art can be added to the emulsion layer according to the present invention. Anion, cation, betaine, nonionic surfactants, thickeners such as carboxymethyl cellulose,
A coating aid such as an antifoaming agent, a chelating agent such as ethylenediamine tetraacetate, a developing agent such as polyhydroxybenzenes and 3-pyrazolidinones such as hydroquinone, catechol and pyrogalose may be contained. In addition, stabilizers such as azaindenes and heterocyclic mercapto compounds, and antifoggants can also be added.

As the binder of the silver halide emulsion layer according to the present invention, water-soluble gelatin alone or in combination with casein, dextrin, gum arabic, polyvinyl alcohol, starch or the like can be used. For water-soluble gelatin, acid-treated gelatin, alkali-treated gelatin,
Any of gelatin derivatives, grafted gelatin and the like can be used.

The low-molecular weight gelatin according to the present invention is a gelatin having an average molecular weight of about 50,000 or less, and is, for example, JP-A-1-
No. 158426, No. 4-340539, No. 8-1
No. 10641 and the like. The low molecular weight gelatin according to the present invention can be produced by the method described in the above-mentioned patent, for example, preferably the enzymatic decomposition treatment. The average molecular weight is about 50,000 or less, preferably about 20,000 or less, particularly preferably about 3,000 to about 20,000.

The low molecular weight gelatin according to the present invention is contained in a silver halide emulsion layer and / or a hydrophilic colloid layer containing a hydrophilic polymer as a binder. The contained layer may be only one layer or a plurality of layers. The addition amount of the low-molecular weight gelatin according to the present invention varies depending on the molecular weight and the kind of the binder of the layer to be added, and is in a wide range from a very small amount of about 1% by weight to 100% by weight of the binder constituting the layer. obtain. When added to the silver halide emulsion layer, the low molecular weight gelatin is added in an amount of 1% by weight to 50% by weight, preferably 2% by weight, based on the amount of the binder constituting the silver halide emulsion layer.
To 30% by weight is preferred.

When a relief image is formed on a glass substrate with high adhesion by curing and development, a large contribution is made to a portion close to the glass substrate, that is, a silver halide emulsion in the vicinity of the glass substrate as a starting point. The present inventors have found that Therefore, in the present invention, the thickness of the silver halide emulsion layer corresponding to 5 × 10 −3 mol of silver halide grains per m ² is defined starting from the surface of the glass substrate. The surface of the glass substrate is not always flat, and the thickness of the silver halide emulsion layer is not always constant due to fluctuations in the coating process or the influence of particulate matter contained in the mask material for exposure. Therefore, the thickness of the silver halide emulsion layer according to the present invention is an average value of 10 or more measured values. The thickness of the silver halide emulsion layer can be measured by a method known to those skilled in the art.A typical method is to cut a resin-embedded glass mask material with a diamond cutter and observe the cross section with an electron microscope. There is a method to measure.

In the present invention, the thickness of the silver halide emulsion layer is 0.5 μm or more and 5 μm or less, and the maximum optical density of the image is 3.0 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 fluctuation of the coating process or the influence of particulate matter contained in the exposure mask material. Therefore, the thickness of the silver halide emulsion layer in the present invention is shown as an average thickness in a size of 10 mm × 10 mm square or more. Also,
The optical density of the relief image depends on the type of image,
For example, in a very fine image, the optical density may be half or less as compared with the large area portion (so-called solid portion). In the present invention, similarly, the maximum optical density means the maximum density of the central portion of a relief image of 10 mm × 10 mm square or more.

The hardening and developing method has the following important behaviors due to the reaction mechanism in which gelatin in the exposed area is crosslinked and hardened. When light is exposed from the surface of the light-sensitive material, the silver halide crystals near the base material are less exposed than the ones near the emulsion layer surface because of light scattering due to silver halide, etc. The film is hard to cure. If the curing in the vicinity of the surface of the base material is insufficient, the image portion may peel off when the uncured non-image portion is removed by washing with water. Therefore, a photosensitive material for curing and development prepared on a thin transparent base material such as a film is generally exposed from the surface opposite to the photosensitive material to the transparent base material. This is called a back shoot.

However, in the exposure mask material of the present invention, glass having a thickness of 5 mm is used as the substrate. In this case, in the back chute, light passes through the glass base material and exposes the photosensitive material to light, but since it is strongly scattered and refracted by the base material, it is difficult to reproduce a fine image. Since it is substantially impossible to carry out backshooting as described above, in the present invention, the sensitivity distribution in the silver halide emulsion layer is controlled by carrying out the following method alone or in plural, and It was found that a more preferable image can be obtained by increasing the sensitivity as compared with the emulsion layer surface. An undercoat layer made of a hydrophilic colloid is provided below the silver halide emulsion layer, a sensitizing dye is contained in the undercoat layer, and the undercoat layer is diffused into the silver halide emulsion layer formed on the upper layer. Further, after the silver halide emulsion layer is prepared, it may be humidified as necessary to enhance the diffusion of the sensitizing dye. An overcoat layer made of a hydrophilic colloid is provided on the upper layer of the silver halide emulsion layer, and a desensitizing substance or a filter dye is added to the upper coating layer and diffused into the silver halide emulsion layer formed below the desensitizing substance or the filter dye. Further, after preparation of the silver halide emulsion layer, humidification may be carried out if necessary to enhance the diffusion of the desensitizing substance or the filter dye. Two or more silver halide emulsions having different sensitivities are prepared, and the light-sensitive layers are formed in order of increasing sensitivity from the lower layer with the glass base material as a starting point.

The metal oxide according to the present invention includes, for example, metal oxides such as colloidal silica, colloidal alumina, titanium oxide, zinc oxide and zirconium oxide, or hydroxides thereof. Colloidal silica is a colloidal substance of amorphous silicic acid anhydride. In addition to being unmodified, the surface of silica is modified with ions and compounds such as ammonia, calcium, and alumina, and the behavior of particles against ionicity and pH fluctuations. A modified colloidal silica having a different value is also included. Colloidal alumina is a colloidal substance having an amorphous or pseudo-boehmite (including boehmite in a broad sense) alumina hydrate having a dispersed shape such as a feather, a fiber, or a plate. Furthermore, 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 mica such as tetrafluorosilicon mica and teniolite, and synthetic inorganic polymer such as 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 it is most easily finely dispersed in a solvent and formed on a transparent substrate. Applied and retained. In this case, the particle size of the finely dispersed metal oxide or hydroxide is about 1 nm to 100 μm. After being coated on a transparent substrate and dried, it may be heated to 150 ° C. or higher in order to enhance the bonding force between the metal oxide particles. Since heating to 600 ° C. or higher causes metal oxide particle growth, it is preferably 150.
It is preferable to heat at not less than 500 ° C and not more than 500 ° C.

The developer used in the developing step for treating the exposure mask material of the present invention includes polyhydroxybenzenes (eg, pyrogallol, catechol, etc.) as a developing agent.
Hydroquinone) is used. Further, development aids, 3-pyrazolidinones, alkaline substances such as potassium hydroxide, sodium hydroxide, lithium hydroxide, sodium triphosphate, or amine compounds, preservatives such as sodium sulfite, viscous agents such as carboxymethyl. Sucrose, antifoggants such as potassium bromide, development modifier,
For example, polyoxyalkylene compound, silver halide solvent such as thiosulfate, thiocyanate, cyclic imide,
Additives such as thiosalicylic acid and mesoionic compounds can be included. The pH of the developer is usually 10-14.
Is.

The step of treating the exposure mask material of the present invention includes the step of removing the silver halide emulsion layer in the non-image area and exposing the glass substrate surface. Since the main purpose is to remove the silver halide emulsion, the processing liquid used in this step contains water as a main component. The treatment liquid may contain a buffer component. In addition, an antiseptic agent may be contained for the purpose of preventing spoilage of the removed gelatin. As a method of removing the silver halide emulsion, a method of scraping with a sponge,
There are a method of peeling off by applying a roller to the film surface and slipping, a method of bringing the roller into contact with the film surface and winding the roller around the film surface. Since physical contact induces pinholes, it is preferable that the step of removing the silver halide emulsion by physical contact is substantially not included. As a preferred embodiment of the post-development processing in the present invention, it is preferable to remove the silver halide emulsion by applying a processing liquid stream to the surface of the silver halide emulsion. As the method of applying the processing liquid stream to the silver halide emulsion surface, a shower method, a slit method, or the like can be used alone or in combination. Also,
It is also possible to increase the efficiency of removal by providing a plurality of showers and slits.

In the present invention, after removing the non-image area silver halide emulsion layer to prepare a relief image, it is treated with a liquid containing a hardening agent well known to those skilled in the art to prepare a stronger relief image. You can As a hardener,
Various substances such as aldehydes such as chrome alum and formalin, ketones such as diacetyl, and mucochloric acid can be used.

[0059]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the invention is not limited thereto as long as the gist of the invention is not exceeded. Example 1 A silver halide emulsion was prepared by the method described in JP-A 2000-310846. After drying the above silver halide emulsion on a glass substrate so as to have a film thickness of 0.3, 3 and 6 μm, and drying, while changing the laser power with an output device using a 532 nm YAG laser as a light source, the beam diameter is changed. 2.
5 μm, 20 μm with image pitch 0.5 μm, and 10
0μm line and space image and 10mm × 1
Output a 0 mm square negative image and a positive image, immerse in the following curing developer (20 ° C) for 1 minute, then soak in 1% acetic acid aqueous solution (20 ° C) for 10 seconds, and further in warm water at 35 ° C for 30 seconds. After dipping, the silver halide emulsion layer was washed off with a sponge and dried to obtain samples (A) to (C).

Curing developer (1) 25 g of sodium hydroxide Hydroquinone 15g 1-phenyl-3-pyrazolidinone 3 g Anhydrous sodium sulfite 5g Make up to 1000 ml with deionized water. pH (25 ° C) = 11.5

On the other hand, Y of 532 nm was added to the silver halide emulsion layer coated on the glass substrate in exactly the same manner as the sample (B).
Beam diameter 2.5μm, image pitch 0.5μ while changing the laser power with an output machine using AG laser
10 m line and space image and 10 m
Output a square negative image and positive image of mx 10 mm,
Development was carried out at 15 ° C. for 3 minutes with a developer GEKORU manufactured by Mitsubishi Paper Mills, followed by fixing at 20 ° C. for 5 minutes with a fixer Diamond Superfix manufactured by Mitsubishi Paper Mills, followed by washing with water and drying to obtain an emulsion mask sample (D).

10 mm × 10 of the above samples (A) to (D)
After measuring the transmission density of the non-image part of the square part of mm,
Using the samples (A) to (D) as originals, a contact printer P-627-GA manufactured by Dainippon Screen Mfg. Co., Ltd. was used to contact-expose the film to a bright room film DCL-EF manufactured by Mitsubishi Paper Mills Ltd. 35 ° C 2 with developer solution
Development was carried out for 0 seconds, fixing was carried out for 30 seconds at 30 ° C. with a fixing solution Diamond Superfix manufactured by Mitsubishi Paper Mills Co., Ltd., washed with water and dried to obtain an image sample. After this, Ushio Denki Co., Ltd., printed wiring board resist printing light source Unirec UMR
UV light was applied to the samples (A) to (D) by using -300.
Minute irradiation, the non-image area transmission density was measured in the same manner, and an image sample was prepared. Ultraviolet light transmission density (λ = 3) at the center of the non-image area of the 10 mm × 10 mm square part of the sample
65 nm) was measured with an ultraviolet-visible absorption spectrophotometer UV-2200 manufactured by Shimadzu Corporation to obtain a non-image part transmission density. The results are shown in Table 1.

In the sample (D), yellow-brown coloring was observed in the non-image area after irradiation with ultraviolet light, and the transmission density in the non-image area increased by 0.15, but in the samples (A) to (C), the non-image There was no change in the partial transmission density. According to the invention,
It was possible to obtain an exposure mask material capable of producing an exposure photomask in which the non-image area was not colored at all by irradiation with ultraviolet rays.

The above samples (A) to (D) were cut with a sharp cutter and the cross section was observed with an electron microscope to confirm that the silver halide grains were uniformly distributed in the silver halide emulsion layer. Then, measure the thickness of the silver halide emulsion layer at 10 points,
The average value was used as the film thickness (μm) of the silver halide emulsion layer. Furthermore, the white light transmission density (density difference from the non-image area) at the center of the image area of the 10 mm × 10 mm square area is calculated as Kol.
Densitometer M from lmorgen Instruments
The maximum transmission density was determined by measuring with acbeth TR-927.

Further, the moistened gauze was placed on the images of the samples (A) to (D) placed horizontally, and the gauze was reciprocated in the horizontal direction under a load of 100 g to observe the peeling of the images. Then, the image strength was visually evaluated by grade as shown below. 1: Peeling of the image occurs, not possible 2: Slight scratches on the surface of the image, but practically acceptable. 3: Good with neither peeling nor scratches. The results are shown in Table 1.

With respect to the image samples of the above samples (A) to (D), the output at which the line width and the space width are equal is judged to be proper exposure, and the image is observed with a 100 times magnifying glass to show the image reproducibility as follows. The grade was evaluated as shown. 1: The image is blurred, not possible 2: The image is reproduced Practically acceptable. 3: The image is reproduced and the line is sharp. 4: The image is reproduced, the lines are very sharp and there are no fringes. The results are shown in Table 1. The numerical value before the arrow shows the image reproducibility evaluation result before the ultraviolet irradiation treatment, and the numerical value after the arrow shows the image reproducibility evaluation result after the treatment.

[0067]

[Table 1]

Example 2 The silver halide emulsion prepared in Example 1 had an average molecular weight of 5
Sample (E) was prepared by adding 10,000 low-molecular-weight gelatin, coating it on a glass substrate so that the silver halide layer has a thickness of 3 μm, and low-molecular-weight gelatin of 0.5 g / m ² and drying. . The average molecular weight of the added low molecular weight gelatin is 30,000, 1.
A sample (F), a sample (G), and a sample (H) were prepared in the same manner as the sample (E) except that the number was 3000.

Samples (E) to (H) were exposed and developed in the same manner as in Example 1 to evaluate the image reproducibility. The results are shown in Table 2.

[0070]

[Table 2]

Example 3 A silver halide emulsion prepared in the same manner as in Example 1 was variously prepared by changing the weight of gelatin per unit weight of silver halide, and each was coated on a glass substrate by changing the coating amount. ,
It was dried to prepare samples (I) to (K).

The samples (B) and (I) to (K) were cut with a sharp cutter and their cross sections were observed with an electron microscope to find that the silver halide grains were uniformly distributed in the silver halide emulsion layer. The thickness of the silver halide emulsion layer was measured at 10 points, and the average value was defined as the thickness X (μm) of the silver halide emulsion layer. In addition, the amount Y (mol / m ² ) of silver halide actually applied was measured with a fluorescent X-ray analyzer system 3270 manufactured by Rigaku Corporation. From these,
The thickness Z (μm) of the silver halide emulsion layer corresponding to 5 × 10 −3 mol of silver halide grains per m ^{2 from the} glass substrate as the starting point was calculated according to the following formula 1. The results are shown in Table 3.
Shown in.

[0073]   Z = 5 × 10−3 × X / Y (Formula 1)

The samples (I) to (K) were exposed, developed and dried in the same manner as in Example 1 to evaluate the mask image strength. The results are shown in Table 3.

[0075]

[Table 3]

Example 4 A silver halide emulsion prepared in the same manner as in Example 1 except that the addition amount of the compound 22 was doubled was coated on a glass substrate to a coating thickness of 1.5 μm and dried. The silver halide emulsion prepared in Example 1 was coated on this layer with a coating thickness of 1.5 μm and dried. After that, exposure and development were performed in the same manner as in Example 1 to obtain a sample (L). The mask image intensity of the sample (L) was evaluated in the same manner as in Example 1. The results are shown in Table 4.

[0077]

[Table 4]

Example 5 On a soda lime glass substrate, colloidal silica Snowtex OUP manufactured by NISSAN CHEMICAL INDUSTRIAL CO., LTD.
m, and dried at room temperature, then at 150 ℃ for 30
Heated for minutes. A silver halide emulsion layer was applied onto this and dried in the same manner as in Example 2 to prepare a sample (M).

An image sample was prepared by treating the sample (M) in the same manner as in Example 1, and the mask image intensity was evaluated in the same manner as in Example 1. The results are shown in Table 5.

[0080]

[Table 5]

Example 6 To a silver halide emulsion prepared in the same manner as in Example 1, hydroquinone and 1-phenyl-3-pyrazolidinone were added to the silver halide emulsion in an amount of 60% by weight and 5% by weight of the silver halide contained in the silver halide emulsion. So that the silver halide layer has a thickness of 3 μm, and is coated on a glass substrate and dried.
An exposure mask material sample (N) was obtained. After exposing the sample (N) in the same manner as in Example 1, the following curing developer (2) was used.
Immerse in (20 ° C) for 1 minute, then 1% acetic acid aqueous solution (20
℃) for 10 seconds, and then in warm water at 35 ℃ for 30 seconds.
After dipping for 2 seconds, the silver halide emulsion layer was washed off with a sponge and dried to obtain a sample (N1). Further, the cured developer (2) obtained by subjecting the sample (N1) to development treatment is subjected to 2
After leaving for a day, the same undeveloped sample (N1) was subjected to the same development treatment to obtain a sample (N2).

Curing developer (2) 25 g of sodium hydroxide Anhydrous sodium sulfite 5g Make up to 1000 ml with deionized water.

Further, a combination of the same undeveloped silver halide emulsion coated sample as used in the preparation of the sample (M) of Example 5 and the cured developing solution (1) of Example 1 was used to prepare the above sample (N1). And the same process as the manufacturing method of (N2),
Samples (O1) and (O2) were obtained.

Image reproducibility of the above samples (N1), (N2), (O1) and (O2) was evaluated in the same manner as in Example 1. The results are shown in Table 6. The value in front of the arrow is the sample (N
1) and (O1), the numbers after the arrows are (N2) and (O
The image reproducibility evaluation result of 2) is shown.

[0085]

[Table 6]

Example 7 A sample obtained by coating and drying a silver halide emulsion in the same manner as in the sample (M) in Example 5 was exposed with an image in the same manner as in Example 1,
Immerse in 20 ° C. developer of Example 1 for 1 minute, then 35
After soaking in warm water at ℃ for 30 seconds, remove from the solution, 3
Hot water at 5 ° C. was sprayed onto the surface of the silver halide emulsion in a shower shape to remove the silver halide emulsion and dried to obtain a sample (P).

The space portions of the line and space images of 20 μm and 100 μm of the sample (P) were observed with a 100 times magnifying glass to examine the residual silver halide emulsion.
No residual was observed even in the space portion of 0 μm.

On the other hand, 100 μm of the samples (M) and (P)
The line part was observed with a 100 times magnifying glass to observe the occurrence of pinholes. With the exposure mask samples (M) and (P),
No pinhole having a diameter of 30 μm or more was observed. The pinhole having a diameter of 30 μm or less was generated in the sample (M), but was not generated in the sample (P). In the current printed wiring board manufacturing process, 30
Although pinholes of μm or less have no problem in practical use, it can be seen that the present invention is extremely effective for coping with future fine patterning.

[0089]

As described above, according to the present invention,
An exposure mask material capable of producing an exposure mask excellent in reproducibility of a fine image could be obtained.

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Claims (7)

[Claims] 1. A mask material for exposure having at least a silver halide emulsion layer on a glass substrate, wherein a relief image is formed by curing and developing treatment, and the film thickness of the silver halide emulsion layer is 0.5 μm or more and 5 μm or less. And the maximum density of the image area is 3 or more. 2. A silver halide emulsion layer and / or a hydrophilic colloid layer having a hydrophilic polymer as a binder, which is optionally provided, contains low molecular weight gelatin having an average molecular weight of 50,000 or less. The mask material for exposure according to 1. 3. The silver halide emulsion layer is 5 × per 1 m ^2.
The thickness of the silver halide emulsion layer containing 103 mol or more of silver halide emulsion grains and corresponding to 5 × 10 −3 mol of silver halide grains per 1 m ^{2 from the} glass base is 2 μm or less. The mask material for exposure according to claim 1 or 2. 4. The mask material for exposure according to claim 1, wherein the sensitivity of the lower layer is higher than that of the upper layer of the silver halide emulsion layer, starting from the glass substrate. 5. The exposure mask material according to claim 1, further comprising a layer composed of a metal oxide between the glass substrate and the silver halide emulsion layer. 6. The exposure according to claim 1, wherein the silver halide emulsion layer and / or the hydrophilic colloid layer, which is optionally provided with a hydrophilic polymer as a binder, contains a curing developer. Mask material. 7. The exposure mask material according to claim 1, wherein the silver halide emulsion in the unexposed portion is removed in a step that does not substantially involve physical contact with a peeling roller or the like.