JP2802805B2 - Silver halide photographic light-sensitive material having a glass support for direct positive - Google Patents

Description

The present invention relates to a direct-positive silver halide photographic material having a glass support.

[Background of the Invention]

Silver halide photographic materials with a glass support have excellent dimensional stability, so they are used as photomask materials for IC manufacturing and display-related photomask materials that require high precision. It is widely used in other fields such as and photo-typesetting.

Such photomasks for manufacturing ICs and display-related photomasks are used repeatedly, and therefore usually require duplication.

In order to make a duplicate, a negative photosensitive material is subjected to reversal development processing as described in Corona Co., Ltd. `` Basics of Photographic Engineering Silver halide photography '', pages 339 to 342, to obtain a positive image,
There is a method of subjecting the fogged direct positive photosensitive material to a normal developing process to obtain a positive image.

Among them, the method using a direct-positive light-sensitive material provided with fog is becoming increasingly popular because of its simple processing and high sensitivity. Further, the silver halide photographic light-sensitive material for direct positive to which such fog has been imparted has recently been moving toward higher sensitivity. In order to achieve high sensitivity, it is necessary to obtain sufficient development activity with as little fog as possible. For this purpose, a method of imparting fog in the presence of a reducing fog agent is advantageously used. As an example of such a fogging method, US Pat. No. 3,501,305,
There are methods described in JP-A-3,501,306 and JP-A-3,501,307.

On the other hand, as described above, in order to faithfully reproduce a high-accuracy image, it is necessary to use a glass having excellent dimensional stability as a support.

Generally, in order to apply a direct positive silver halide emulsion containing silver halide grains provided with fog in the presence of a reducing fogging agent to a glass support, the surface of the glass is treated with stannic chloride or the like. As an undercoat layer, for example, a layer containing an inorganic compound such as chromium alum in gelatin is provided, and a silver halide emulsion is coated thereon to maintain adhesion to a glass support. General.

However, in such a method, the adhesion to the glass substrate is insufficient, and the emulsion layer is easily peeled off when it comes into contact with another dry plate during the current processing, causing damage to the pattern image or reducing the image contrast. This has the disadvantage of lowering the character quality and inferior character quality.

[Object of the invention]

An object of the present invention is to solve the above-mentioned problems of the prior art,
An object of the present invention is to provide a direct-positive silver halide photographic material having high sensitivity, high contrast, and in which a silver halide emulsion layer on a glass support is not peeled off during development and is hardly damaged after development processing. .

[Configuration of the invention]

As a result of intensive studies, the present inventors have found that the object of the present invention is to provide at least one silver halide emulsion layer for direct positive containing silver halide grains provided with fog in the presence of a reducing fog agent on a glass support. The direct positive silver halide photographic light-sensitive material comprises a silane coupling agent in a constituent layer on the side of the silver halide emulsion layer for direct positive on a glass support. It has been found that this can be achieved by a silver halide photographic light-sensitive material. The amount of the hydrophilic colloid contained in the constituent layer on the side of the direct positive silver halide emulsion layer is preferably 4 g or more and less than 12 g per 1 m ² .

 Hereinafter, the present invention will be described in more detail.

The direct-positive silver halide photographic light-sensitive material of the present invention has a support as a glass support, and contains silver halide grains provided with fog in the presence of a reducing fog agent on the glass support. It is provided with at least one direct positive silver halide emulsion layer.

Such a technique for imparting fog in the presence of a reducing fog agent is described in, for example, U.S. Pat.
It is described in each specification such as 3,501,306 and 3,501,307.

More specifically, examples of the reducing fog agent used for imparting fog in the present invention include formalin, hydrazine, polyamide (eg, triethylenetetramine, tetraethylenepentamine, etc.), thiourea dioxide, tetrahydroxymethylphosphonium chloride ,
There are amine borane, borohydride compound, stannous chloride, etc., generally 10 ^-7 to 10 ^-3 per mol of silver halide.
It is preferable to use it in the molar range. These reducing fog agents may be used alone or in combination of two or more. Moreover, you may use together with a water-soluble gold compound.

The silver halide emulsion used in the present invention may have any grain size, crystal habit, silver halide composition, and the like. Among those useful as a photographic material, those having a grain size of about 0.1 to about 1 .mu.m have graininess and sharpness. It is preferable in terms of properties. These silver halide emulsions are prepared by various methods. For example, U.S. Patent No. 2,717,833, JP-B-43-4125, and British Patent 1,1
No. 86,717 and the like, a method of incorporating a Group 8 soluble gold complex salt, a method of preparing an ammoniacal emulsion as described in U.S. Pat. No. 2,184,013, U.S. Pat.
No. 501,305, a monodisperse emulsion preparation method, a heterodispersion emulsion preparation method as described in JP-A-49-46327, a regular grain emulsion preparation as described in U.S. Pat. Method, US Patent 3,36
No. 7,785, British Patent Nos. 1,229,868 and 1,186,718 and the like, and a method such as an internal latent image type emulsion preparing method described in US Pat. No. 2,592,250 described in U.S. Pat.

The silver halide emulsion of the present invention uses a noble metal salt such as a rhodium salt (including a complex salt) or an iridium salt (including a complex salt) such as a rhodium salt (including a complex salt), which is called an internal electron acceptor, in order to directly obtain a positive image. Organic desensitizers adsorbed on the grain surface can be contained individually or in combination.

Next, the silver halide photosensitive material for direct positive of the present invention is:
A silane coupling agent is contained in the structure on the side of the silver halide emulsion layer for direct positive on the glass support. Therefore, the silane coupling agent is directly contained on the same surface as the positive silver halide emulsion layer, but the silane coupling agent does not necessarily need to be contained in the emulsion layer. Preferably, a silane coupling agent is contained in the emulsion layer (when there are two or more direct positive silver halide emulsion layers, any one of them).

Hereinafter, the silane coupling agent used in the present invention will be described.

The silane coupling agent used in the present invention is optional, but is preferably a compound represented by the following general formula [S].

General formula [S] In the formula, X ₃ represents an oxygen atom or —O—CO—. R ₁₁ , R
_12, R ₁₃ and R ₁₄ each represent a halogen atom or an optionally substituted hydrocarbon group. At least one of R ₁₁ to R ₁₄ is a double bond, a halogen atom, an epoxy group, an acid anhydride residue, an alkoxycarbonyl group or amino group. n ₁ , n ₂ and n ₃ each represent 0 or 1, and n ₁ + n ₂ ,
n ₁ + n ₃ is at least 1.

In the general formula [S], examples of the halogen atom represented by R _{11 to} R ₁₄ include a fluorine atom, a chlorine atom,
The hydrocarbon group which may be substituted includes a bromine atom, an iodine atom and the like, and includes a saturated and unsaturated chain-like and cyclic group, for example, an alkyl group (eg, methyl, ethyl, propyl, etc.), an alkenyl group Groups (eg, vinyl, allyl, etc.) and aryl groups (eg, phenyl, tolyl, etc.).

The double bond possessed by at least one of R _{11 to} R ₁₄ is
C = C bond, for example, alkenyl group, acryloyl group,
Introduced as a methacryloyl group, a vinylcarbonylamino group, an isopropenylcarbonylamino group, etc., examples of the acid anhydride residue include a group such as a methylcarbonyloxycarbonylethyl group, and a halogen atom is, for example, a haloacylamino. It may be introduced in the form of a group.

Preferred specific examples of the compound represented by formula (S) are shown below, but it should not be construed that the invention is limited thereto.

_{(S-2) CH 2 =} CH-Si (OCOCH 3) 3 _{(S-5) NH 2 (} CH 2) 2 NH (CH 2) 3 -Si (OCH 3) 3 (S-6) Cl (CH 2) 3 -Si (OCH 3) 3 _{(S-9) CH 2 =} CHCONH (CH 2) 3 -Si (OC 2 H 5) 3 (S-10) ClCH 2 CONH (CH 2) 3 -Si (OC 2 H 5) 3 (S-11) _{CH 2 = CH-Si (OC} 2 H 5) 3 (S-13) CH ₂ CHCH—SiCl _{3 The} compound represented by the general formula (S) is disclosed in JP-B-48-35656.
And can be obtained as a commercial product from Toray Silicon Co., Ltd. or Chisso Co., Ltd.

When the compound is added to a hydrophilic colloid layer such as a silver halide emulsion layer, it is preferable to add the compound by dissolving it in water, lower alcohol, acetone or the like. The addition amount is preferably in the range of 5 × 10 ^-6 to 1 × 10 ^-2 mol per gram of the hydrophilic colloid.
More preferably, it is in the range of 1 × 10 ^{−5 to} 5 × 10 ⁻³ mol.

As a constituent layer of the direct positive silver halide emulsion layer containing silver halide grains of the present invention, at least one direct positive emulsion layer is required, and if necessary, a protective layer and an emulsion layer are provided on the emulsion layer. An undercoat layer can be provided below the layer.

In the present invention, a hydrophilic colloid of 4 g or more and less than 12 g, preferably 5 g or more and less than 10 g per 1 m ² is contained in the constituent layer on the side of the direct positive silver halide emulsion layer.

Above constituting content 1 m ² per 4g of hydrophilic colloid in the stratified
If it is less than 1, the contrast of the obtained image is high, but the image is easily scratched after the development processing. If the amount is more than 12 g, scratches are less likely to occur, but the contrast is reduced, and the product is not practical.

The hydrophilic colloid used in the hydrophilic colloid layer such as a silver halide emulsion layer in the light-sensitive material of the present invention includes:
Examples include gelatin, albumin, zein, casein, alginic acid, cellulose derivatives (eg, hydroxyethyl cellulose, carboxymethyl cellulose, etc.), synthetic hydrophilic colloids (eg, polyvinyl alcohol, poly-N-vinylpyrrolidone, etc.). Preferred hydrophilic colloids include gelatin. Two or more hydrophilic colloids can be used in combination.

The glass support used in the present invention is not particularly limited in glass composition, but is preferably soda-lime glass, soda-lime aluminum glass, or the like.

In addition, in order to enhance the flatness of the glass support, a glass manufactured by a so-called float method in which a molten glass is manufactured on a bath of a molten metal tin solution while controlling the desired thickness and flatness. A support can be preferably used.

It is preferable that the surface of the support is pre-degreased and pre-treated to improve hydrophilicity before the surface treatment with the silane coupling agent and the application of the hydrophilic colloid layer coating solution as described above. The end face of the support is preferably polished for handling.

In the light-sensitive material of the present invention, a backing layer containing a light-absorbing dye can be provided on the side opposite to the silver halide emulsion layer. Any dye can be selected as the light absorbing dye.

Other photographic additives can also be used in the direct positive silver halide photographic emulsion used in the present invention.

The silver halide emulsion of the present invention can be optically sensitized to a desired wavelength range using a dye known as a desensitizing dye in the photographic industry. Although the desensitizing dye may be used alone,
Two or more kinds may be used in combination. Further, dyes known as sensitizing dyes may be combined in the emulsion.

The light-sensitive material of the present invention may contain other appropriate additives. For example, the stabilizer may include triazoles, azaindenes, quaternary benzothiazolium compounds, mercapto compounds, or water-soluble inorganic salts such as cadmium, cobalt, nikesol, manganese, gold, potassium, and zinc. For example, formalin as a hardening agent,
Aldehydes such as glyoxal and mucochloric acid, s-
Triazines, epoxies, aziridines, vinyl sulfonic acid, etc .; and as coating aids, for example, savonin, sodium polyalkylene sulfonate, lauryl or oleyl monoether of polyethylene glycol, amylated alkyltaurine, fluorine-containing compounds, etc. For example, a polyalkylene oxide and a derivative thereof may be contained as a sensitizer. Further, a color coupler can be contained. In addition, a preservative, an antistatic agent, a developer and the like can be contained as required.

As the developer for processing the light-sensitive material of the present invention, those having a commonly used composition can be used. Examples of the developing agents include: ぱ, hydroquinone, alkylhydroquinone (eg, methylhydroquinone, dimethylhydroquinone, t-butylhydroquinone), catechol, pyrazole, chlorohydroquinone, dichlorohydroquinone, methoxyhydroquinone, ethoxyhydroquinone, aminophenol developing agents (eg, N-methyl-p
-Aminophenol, 2,4-diaminophenol), ascorbic acid developing agent, N-methyl-p-aminophenol sulfate, pyrazolones (eg, 4-aminopyrazolone), 3-pyrazolidone developing agent (eg, 1-phenyl-3- Pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-5-methyl-
3-pyrazolidone, 1-phenyl-4-methyl-3-lazolidone, 1,5-diphenyl-3-pyrazolidone, 1-
p-tolyl-3-pyrazolidone, 1-p-hydroxyphenyl-4,4-dimethyl-3-pyrazolidone) and the like are used alone or in combination.

In the developing solution, if necessary, preservatives such as sulfites, bisulfites, and hydroxylamines; alkaline agents such as hydroxides, carbonates, and phosphates; pH adjusters such as acetic acid; polyethylene glycols Sensitizers such as quaternary ammonium salts; organic solvents such as methanol, diethylene glycol, diethanolamine, dimethylformamide and dimethyl sulfoxide; development accelerators; surfactants;
Antifoaming agent; color tone agent; viscosity-imparting agent such as carboxymethylcellulose and hydroxyethylcellulose; hardening agent such as glutaraldehyde; silver sludge inhibitor; thioether;
Silver halide solvents such as thioamide, thiocyanate and thiosulfate; antifoggants such as potassium bromide and benzotriazole; various additions such as chelating agents such as aminopolycarboxylic acid, aminopolyphosphonic acid and phosphonocarboxylic acid An agent can be contained.

As the fixing solution used for processing the light-sensitive material of the present invention, those having a commonly used composition can be used. Sodium thiosulfate, ammonium thiosulfate, sodium thiocyanate, ammonium thiocyanate as a fixing agent, thiourea as a silver halide solvent, amine derivatives, etc., as well as sodium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, etc. Sulfites; borate such as boric acid, borax, sodium metaborate;
Organic carboxylic acids such as acetate, citric acid, tartaric acid, and malic acid; inorganic acids such as sulfuric acid and hydrochloric acid; amines such as ethylenediamine, jetanolamine, and triethanolamine; potassium alum, ammonium amber, aluminum sulfate, and chloride Water-soluble aluminum salts such as aluminum; organic compounds such as methanol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polyoxyethylene glycol, and acetone, and, if necessary, iodides such as potassium iodide and sodium iodide; Other additives can be included.

〔Example〕

Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto.

Example 1 (Preparation of Emulsion Coating Solution) A silver chlorobromide gelatin emulsion of 31 mol% of silver bromide was prepared by a reverse mixing method so as to contain 2.0 × 10 ⁻⁴ mol of rhodium chloride / 1 mol of silver during grain formation. Physical ripening was performed at 39 ° C for 20 minutes. The emulsion thus prepared was desalted by a conventional method, and gelatin was added to obtain a cubic emulsion having an average particle size of 0.2 μm.

The above emulsion was adjusted to pH = 6.0, and after adding 850 mg of potassium iodide and 280 mg of potassium bromide per mol of silver halide, 150 mg of formalin was added per mol of silver halide and ripened at 60 ° C. for 60 minutes. Then, 850 mg of potassium iodide and 460 mg of potassium hydroxide were added per mole of silver halide, and the mixture was aged at 60 ° C. for 110 minutes to produce reduced fog.

 After aging, the pH is adjusted to 6.5 with citric acid.

The following compounds [A], [B], [C], [D], [E], as additives are added to the fogged emulsion.
[F], [G], potassium bromide, triethyltetramine, saponin, the following compound [H] as a hardener and the silane coupling agent according to the present invention are shown in Table 1.
Was added as shown.

Compound [H] (CH ₂ CHCHSO ₂ CH _{2 2} O (Preparation of Subbing Solution) Methanol and chromium ban as a hardening agent were added to an aqueous gelatin solution.

(Preparation of Backing Coating Solution) The following compound [I] was added as a binder to a mixed solvent of methanol and ethanol, and the following compounds [J], [K] and [L] were added as light absorbing dyes.

(Preparation of sample) The above coating solution was coated on the surface (bottom surface) of the float glass support which was in contact with the metal tin bath during the manufacture of the float glass.
The photosensitive material samples Nos. 3 to 9 were prepared by applying the combinations shown in FIG. At that time, the emulsion layer was coated so as to have a silver amount of 2.5 g / m ² .

For comparison, a coating solution having a formulation in which the silane coupling agent was removed from the above emulsion formulation was applied to prepare photosensitive material No. 1.

Further, after applying and drying the undercoating liquid on the bottom surface of the float glass support, a coating liquid having a formulation obtained by removing the silane coupling agent from the above emulsion formulation was applied onto the undercoating layer. .2 was created.

Samples were prepared as shown in Table 1 for the amount of gelatin as a hydrophilic colloid in the undercoat layer and the emulsion layer on the emulsion layer side.

The sample illuminated in this way was placed at 50 ° C. and 80% RH for 6 hours.
Time seasoned. The film was immersed in the following developer-1 at 20 ° C. for 5 minutes. After the emulsion film was wet, the emulsion film was scratched with the tip of tweezers, and the surface was rubbed with a finger to evaluate the adhesion to glass.

 The adhesiveness was evaluated on a three-point scale. ：: No problem, Δ: Scratched ×: Film peeling occurred.

The obtained sample was subjected to wedge exposure using a tungsten lamp through a Kodak Wratten filter, and the following treatment was carried out using a developing solution-1 and a fixing solution having the following composition. The results of measurement of the developed sample using a densitometer of Konica PD-65 (manufactured by Konica Corporation) were also examined.

The sensitivity is a relative sensitivity based on the exposure amount to obtain a density of 2.5.

The contrast was indicated by tan θ between two points of density 0.3 and 2.5.

The easiness of scratching after the development process is 6 at 50 ° C and 80% RH.
After performing the seasoning for a long time, use the HEIDON
Using a -18 type mold, the load was measured when the emulsion layer was peeled off the glass support while gradually applying a load.
The larger the value of the load, the less likely it is to scratch.
The following is not practical.

 The results are shown in Table 1.

<Development> Development 20 ° C 3.5 minutes Fixing 20 ° C 2 minutes Washing 20 ° C 5 minutes Drying Natural drying <Developer-1> Hydroquinone 20 g Potassium sulfite 5 g Sodium ethylenediaminetetraacetate 1 g Potassium carbonate 35 g Sodium carbonate 15 g Potassium bromide 3 g Nitroindazole 4 mg Triethylene glycol 30 g Diethanolamine 20 g Formalin sodium bisulfite adduct 50 g Polyethylene glycol (average molecular weight 1500) 0.2 g Water was adjusted to 1 and pH was adjusted to 10.2 with sodium hydroxide.

<Fixing solution formulation> (Composition A) Ammonium thiosulfate (72.5% W / V aqueous solution) 20mg Sodium sulfite 17g Sodium acetate trihydrate 6.5g Boric acid 6g Sodium citrate dihydrate 2g Acetic acid (90% W / V aqueous solution) 13.6 g (Composition B) Pure water (ion-exchanged water) 17 mg Sulfuric acid (50% W / V aqueous solution) 4.7 g Aluminum sulfate (aqueous solution with an equivalent content of Al ₂ O ₃ of 8.1% W / V) 26.5 g When using fixer The above composition A and composition B were dissolved in 500 ml of water in this order, and finished to 1 for use.

 The pH of the fixing solution was about 4.3.

As can be seen from Table 1, Sample No. 2 having a gelatin subbing layer hardened with a chromium bang has a sufficient sensitivity, but has a problem in the adhesion between the emulsion layer and the glass, and The contrast is greatly reduced. Even if the addition of the silane coupling agent in the emulsion layer, the amount of gelatin as the hydrophilic colloid sample No.3 of less than 4g / m ² is contrast high, easily scratched after development processing, unpractical . Further, Sample No. 4 having a density of 12 g / m ² or more has no problem of susceptibility to scratching, but has a low contrast and is a practical problem.

On the other hand, it can be seen that Sample Nos. 5 to 8 of the present invention have high sensitivity and contrast, good adhesion between the emulsion layer and glass, and are hardly damaged after the development processing.

Example 2 The reducing fog agent of the photosensitive material prepared in Example 1 was changed from formalin to 0.15 g of thiourea dioxide, and the following developer was used.
Except for the treatment in step 2, exposure and
Do the processing. A measurement was taken.

 Table 2 shows the results.

<Developer-2> Pure water Approx. 800 ml Potassium sulfite 60 g Ethylenediaminetetraacetic acid disodium salt 2 g Potassium hydroxide 10.5 g 5-methylbendtriazole 300 mg Diethylene glycol 25 g 1-phenyl-4,4-dimethyl-3-pyrazolidinone 300 mg 1-phenyl -5-Mercaptotetrazole 60mg Potassium bromide 3.5g Hydroquinone 15g Potassium carbonate 15g Pure water (ion-exchanged water) is added to make up to 1000ml.

 The developer pH was about 10.8.

As can be seen from Table 2, Sample No. 10 having a gelatin subbing layer hardened with a chrome light bang had sufficient sensitivity, but had a problem in adhesion between the emulsion layer and glass, and The contrast is greatly reduced.

Even if the addition of the silane coupling agent in the emulsion layer, the amount of gelatin as the hydrophilic colloid 4g / m ² less than the sample N
Although o.11 has high contrast, it is easily scratched after development processing and is not practical. Further, Sample No. 12 of 12 g / m ² or more has no problem of susceptibility to scratching, but has a low contrast and is a practical problem.

On the other hand, it can be seen that Samples Nos. 13 to 16 of the present invention have high sensitivity and contrast, good adhesion between the emulsion layer and glass, and are hardly damaged after the development processing.

〔The invention's effect〕

According to the present invention, it was possible to provide a silver halide photographic material having high sensitivity, high contrast, excellent adhesion to a glass support, and resistant to damage even after development processing.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁶ , DB name) G03C 1/485 G03C 1/76 G03C 1/43

Claims (2)

(57) [Claims] 1. A direct positive silver halide having at least one silver halide emulsion layer for direct positive containing silver halide grains provided with fog in the presence of a reducing fogging agent on a glass support. A silver halide direct-positive photographic material comprising a silane coupling agent in a constituent layer on the side of a silver halide emulsion layer for direct positive on a glass support. 2. The method according to claim 1, wherein the amount of the hydrophilic colloid contained in the constituent layer on the side of the direct positive silver halide emulsion layer containing silver halide grains is 4 g or more and less than 12 g per m ^2. 2. The silver halide photographic material for direct positive use according to item 1.