JPH04242240A - Silver halide photographic sensitive material having float glass support - Google Patents

Abstract

PURPOSE:To prevent peeling of both of a silver halide emulsion layer and an antihalation layer at the time of peeling a tape by surface treating the glass support with fluoride, then coating the surface of a tin layer with a silver halide emulsion layer and the surface on the air side with an antihalation layer. CONSTITUTION:The tin surface of the float glass support surface-treated with fluoride is coated with the silver halide emulsion layer containing a silane coupling agent and the surface of the glass support in the air side is coated with the antihalation layer containing a light absorbing dye, thus permitting adhesion of the glass support to the emulsion layer and to the antihalation layer to be improved.

Description

[Detailed description of the invention]

0001

[Field of Industrial Application] The present invention relates to a silver halide photographic light-sensitive material, and more specifically, the present invention relates to a silver halide photographic light-sensitive material. This invention relates to a silver halide photographic material with improved adhesion between a layer and a glass support.

0002

Background of the Invention Silver halide photographic light-sensitive materials having a glass support have excellent stability, so they can be used as photomask materials for the manufacture of ICs that require precision, as well as photomasks for photometry, typesetting, and display-related applications. It is used as. Especially regarding display-related photomasks,
Along with the trend toward higher definition, larger sizes are also progressing, and photosensitive materials for photomasks are naturally required to be larger in size. Since such a glass support is required to have a high degree of flatness, it is advantageous to manufacture it by a float method.

[0003] The glass support manufactured by this float method is a method in which the desired plate thickness and flatness can be obtained by pulling molten glass while slowly cooling it on a molten tin tank. One side of the glass support manufactured by this method always comes into contact with molten tin when passing through a tin bath, resulting in glass with tin attached to the glass surface (this side is called the tin side, and the other side is air-filled). (referred to as surface or air surface)

0004
] A method of coating a silver halide emulsion on the air surface of such a float glass support was disclosed in Japanese Patent Application No. 1986-5.
No. 3453 is known. In this method, when a display mask is produced, a crater-shaped black foreign substance is exposed on the glass surface in the non-image area. (This foreign material is caused by evaporation of molten tin in the tin tank, oxidation, and agglomeration into tin oxide, which falls onto the air surface of the molten glass and forms a crater-shaped black foreign material.) This foreign matter cannot be removed with a needle or the like, so if black foreign matter occurs, it becomes a defective mask and poses a big problem.

In order to avoid this problem, JP-A-1-255855 discloses a method of coating a silver halide emulsion on the tin surface of a float glass support. Although this method does not have the above-mentioned problem of crater-like foreign matter, since metal tin is present in a thin layer on the glass surface, even if the organic silane coupling agent disclosed in Japanese Patent Publication No. 48-3565 is used, The hydrophilic colloid layer had insufficient properties, and when an adhesive tape was attached to the surface to remove foreign matter adhering to the surface after development and then peeled off, the hydrophilic colloid layer peeled off.

On the other hand, the antihalation layer on the air side also
This method has the disadvantage that when removing foreign matter from the surface with an adhesive tape or the like, the film peels off and the anti-halation function is lost. As a result of intensive research to solve these drawbacks, after the surface of the float glass support was treated with fluoride,
It has been found that by coating a silver halide emulsion layer on the tin side and coating an antihalation layer on the air side, the adhesion between these layers and glass can be improved.

[0007]

OBJECTS OF THE INVENTION Therefore, it is an object of the present invention to provide a silver halide photographic material in which the silver halide emulsion layer on a float glass support does not peel off due to tape peeling after development processing, and the antihalation layer also does not peel off with tape. It's about doing.

[0008]

SUMMARY OF THE INVENTION The above-mentioned object of the present invention is to provide a silver halide photographic material having a silver halide emulsion layer on the tin surface of a float glass substrate surface-treated with fluoride. This is achieved by a silver halide photographic light-sensitive material which contains a silane coupling agent in the support and has an antihalation layer containing a light-absorbing dye on the air side of the float glass support.

The fluoride used in the surface treatment of the glass substrate in the present invention is a compound with hydrogen, ammonium, an alkali metal, or an alkaline earth metal, and particularly preferred is H.
F, NaF, KF, NH4 F, BeF2, MgF2
, BaF2. The above-mentioned fluorides may be used alone or in arbitrary mixtures. The concentration of fluoride is arbitrary, but a concentration of 0.001% to 30% is preferred.

The fluoride can be diluted with any solvent such as water, methanol, ethanol, sulfuric acid, hydrochloric acid, nitric acid and the like. The surface treatment method is performed by immersing the glass substrate in the above-mentioned fluoride. At that time, the surface may be cleaned with a sponge or brush. The surface treatment time may be any time depending on the concentration of the solution used. The silane coupling agent used in the present invention is preferably a compound represented by the following formula 1.

[0011]

[Formula 1]

In the formula, X represents an oxygen atom or -O-CO-. R11, R12, R13 and R14 each represent a halogen atom or a hydrocarbon group (including substituted hydrocarbon groups), and at least one of R11 to R14 is a double bond, a halogen atom, an epoxy group, or an acid anhydride. residues, alkoxycarbonyl groups or amino groups. n, n' and n'' each represent 0 or 1, and n+n'+n'' is at least 1.

In the above formula 1, the hydrocarbon groups (including substituted hydrocarbon groups) represented by R11 to R14 include saturated and unsaturated chain and cyclic groups, such as alkyl groups (for example, methyl, ethyl, propyl, etc.), alkenyl groups (e.g. vinyl, allyl, etc.)
, aryl groups (eg, phenyl, tolyl, etc.), and the like.

The double bond that at least one of R11 to R14 has is a C═C bond, which is introduced as an alkenyl group, an acryloyl group, a methacryloyl group, a vinylcarbonylamino group, an isopropenylcarbonylamino group, etc. Examples of the group include a methylcarbonyloxycarbonylethyl group, and a halogen atom may be introduced in the form of a haloacylamino group. Preferred specific examples of the compound represented by Formula 1 are shown below, but the invention is not limited thereto.

[0015]

[Chemical formula 1]

[0016]

[Case 2]

[0017]

[Chemical formula 3]

[0018] The compound represented by formula 1 is
It can be synthesized by the method described in Japanese Patent No. 65, and can also be obtained as a commercial product from Toray Silicon Co., Ltd. or Chisso Corporation. The silane coupling agent may be added to any hydrophilic colloid layer such as the silver halide emulsion layer, subbing layer, or protective layer, or the glass surface may be treated with the compound.

Preferably, the silane coupling agent is contained in a silver halide emulsion and coated, or the surface of the glass support is treated with the silane coupling agent. More preferably, the silane coupling agent is mixed with a halogen This is an embodiment in which it is contained in a silveride emulsion and coated. The latter embodiment has the advantage that the manufacturing process of the photosensitive material is simple.

When the oxide is added to a hydrophilic colloid layer such as a silver halide emulsion layer, it is preferably added after being dissolved in water, lower alcohol, acetone, or the like. The amount added is 2 x 10-5 to 8 x 10-4 per gram of hydrophilic colloid.
A molar range is preferred.

When treating the glass surface with the compound, a solution dissolved in a solvent may be applied to the glass surface by dipping, showering, etc. in the same manner as described above. The amount applied to the glass surface is preferably in the range of 6 x 10-5 to 2 x 10-3 mol/m2.

Hydrophilic colloids used in the hydrophilic colloid layer such as the silver halide emulsion layer provided on the tin side of the support in the light-sensitive material of the present invention include gelatin, albumin, zein, casein, alginic acid, cellulose derivatives ( Examples include hydroxyethylcellulose, carboxymethylcellulose, etc.), synthetic hydrophilic colloids (eg, polyvinyl alcohol, poly-N-vinylpyrrolidone, etc.), and the like.

The silver halide emulsion of the silver halide emulsion layer used in the present invention contains conventional silver halide such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride. Any grains used in silver halide emulsions can be used, and there are no restrictions on the grain size and grain size distribution of the silver halide grains. An emulsion containing 10 mol% or less of silver chlorobromide or silver chloroiodobromide and a grain size of 0.1 to 1.0 μm, and silver iodide of 8
The present invention can be applied at least to Lippmann type emulsions containing silver iodobromide in an amount of mol % or less and having a grain size of 0.1 μm or less, and direct positive emulsions which are fogged in the presence of a reducing fogging agent.

[0024] The float glass support used in the present invention is
Although there are no particular limitations on the glass composition, soda lime glass, soda lime aluminum glass, and the like are preferred. The surface of the support is preferably degreased and pretreated to improve hydrophilicity before surface treatment with the fluoride. In addition, it is preferable for the end face of the support to be polished in terms of handling.

The light-sensitive material of the present invention has at least one layer on the tin side of the float glass support surface-treated with fluoride.
It has a silver halide emulsion layer and an antihalation layer containing a light-absorbing dye on the air side of the float glass support. A subbing layer or the like can be provided below the protective layer and emulsion layer. Furthermore, a light-absorbing dye can also be incorporated into the silver halide emulsion layer.

[0026] The silver halide grains used in the silver halide emulsion layer according to the present invention are formed through the process of grain formation and/or
Or, during the growth process, at least one selected from cadmium salts, zinc chlorides, lead salts, thallium salts, iridium salts (including complex salts), rhodium salts (including complex salts), and iron salts (including complex salts) is used. By adding metal ions to the particles, these metal elements can be contained inside the particles and/or on the particle surfaces, and by placing them in an appropriate reducing atmosphere, reduction sensitizing nuclei can be formed inside the particles and/or on the particle surfaces. can be granted.

[0027] Unnecessary soluble salts may be removed from the silver halide emulsion of the silver halide emulsion layer according to the present invention after the growth of silver halide grains is completed, or they may be left in the silver halide emulsion layer. When removing the salts, Research Disclosure
osure) No. 17643.

The silver halide emulsion used in the present invention is
Chemical sensitization can be carried out by conventional methods. That is, a sulfur sensitization method, a selenium sensitization method, a reduction sensitization method, a noble metal sensitization method using gold or other noble metal compounds, etc. can be used alone or in combination. The silver halide emulsion used in the present invention can be optically sensitized to a desired wavelength range using a dye known as a sensitizing dye in the photographic industry. The sensitizing dyes may be used alone or in combination of two or more. A supersensitizer may be included in the emulsion together with the sensitizing dye.

The silver halide emulsion used in the present invention may be subjected to chemical ripening for the purpose of preventing fog during the manufacturing process, storage or photographic processing of light-sensitive materials, or to maintain stable photographic performance. At the end and/or after chemical ripening, compounds known in the photographic industry as antifoggants or stabilizers can be added before coating the silver halide emulsion.

The photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material of the present invention contain a binder (or protective colloid).
Hardening can be achieved by using one or more hardening agents that crosslink molecules and increase film strength. The hardening agent can be added in an amount capable of hardening the photosensitive material to such an extent that it is not necessary to add the hardening agent to the processing solution, but it is also possible to add the hardening agent to the processing solution.

A plasticizer may be added to the silver halide emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material of the present invention for the purpose of increasing flexibility. The photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material of the present invention may contain a dispersion (latex) of a water-insoluble or poorly soluble synthetic polymer for the purpose of improving dimensional stability.

The silver halide emulsion layer of the light-sensitive material of the present invention contains polyalkylene oxide or its ether, ester, etc. for the purpose of increasing sensitivity, increasing contrast, or promoting development.
It may also include derivatives such as amines, thioether compounds, thiomorpholines, quaternary ammonium compounds, urethane derivatives, urea derivatives, imidazole derivatives, and the like.

A matting agent is added to the silver halide emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material of the present invention for the purpose of reducing the gloss of the light-sensitive material, improving the ease of writing, improving the vacuum adhesion between dry plates, etc. can be added. Preferably, the alkali-soluble matting agent described in Japanese Patent Application No. 63-207588 is used.

An antistatic agent can be added to the photosensitive material of the present invention. The antistatic agent may be used in the antistatic layer on the side of the support on which the emulsion is not laminated, and the antistatic agent may be used in the antistatic layer on the side of the support on which the emulsion is not laminated.
Alternatively, it may be used in a protective colloid other than the emulsion layer on the side where the emulsion layer is laminated on the support.

The silver halide emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material of the present invention has properties such as coating properties, antistatic properties, slip properties, emulsification dispersion, adhesion prevention, and photographic properties (
Various surfactants can be used for the purpose of improving development acceleration, hardening, sensitization, etc.).

When coating the photosensitive material of the present invention, a thickener may be used to improve coating properties. In addition, for substances such as hardeners, which have quick reactivity and may cause gelation before coating if added to the coating solution in advance,
It is preferable to mix immediately before coating using a static mixer or the like.

For the development of the light-sensitive material of the present invention, hydroquinone is used as a developing agent, and any known method can be used, including development with a Lith developer (infectious developer) having a low concentration of sulfite ions.

[0038]

[Examples] The present invention will be specifically explained below with reference to Examples, but the embodiments of the present invention are not limited thereto. Example 1

[Preparation of silver halide emulsion] Sodium thiosulfate was added to a Lippmann type silver halide emulsion containing 4 mol % of silver iodide and 96 mol % of silver bromide and having an average grain size of 0.05 μm, and the emulsion was then chemically sensitized. , after adding Compound A with the following structure as a sensitizing dye, adding Compound B with the following structure as an inhibitor, adding Compound C with the following structure as a development accelerator, and adding Compound D with the following structure as a hardening agent, The silane coupling agent used in the present invention was added as shown in Table 1.

[Preparation of backing coating solution] In a mixed solvent of methanol and ethanol, add 370 mg of Compound E having the following structure as a binder, 60 mg of Compound F having the following structure as a light-absorbing dye, 30 mg of Compound G, and 4 mg of Compound H.
2 mg and 1 ml of methyl cellosolve were added per m2 each.

[Preparation of Samples] The above-mentioned coating solutions were coated on both sides of a float glass support in the combinations shown in Table 1 to produce samples 1 to 6 of photosensitive materials. At that time, the emulsion layer was coated so that the amount of gelatin was 5.9 g/m2 and the amount of silver was 2.8 g/m2.

Table 1 Sample No.
emulsion layer
Backing layer Fluoride Silane coupling agent Coated surface Fluoride Coated surface Treatment *1
Type Addition amount *2
Processing 1 (comparative example)
None − −
Air side None Tin side 2 (comparative example)
None (4) 9.1
Air side None Tin side 3 (comparative example)
Yes (4) 9.1
Air side Yes Tin side 4 (comparative example) None (4) 9.1
Tin side Yes Air side 5
(This invention) Yes (4) 9.1
Tin surface Yes Air surface 6 (present invention) Yes (9) 9
．． 1 Tin surface Yes
Air side *1 Immerse in HF-0.05% for 2 minutes. *2 Indicates g/mole of silver. *3 Three-level evaluation 〇: No problem △: Slightly peeling ×: Peeling *4 Evaluation area: 20″×
24″

[0043]

[C4]

[0044]

[C5]

Samples 1 to 6 thus obtained were developed at 20° C. for 5 minutes using the following developer-1, followed by fixing, washing with water, drying, and then peeling off the emulsion layer with an adhesive tape. The gender was evaluated.

[Developer-1] Hydroquinone

5g monomethyl-p-aminophenol sulfate
1g anhydrous sodium sulfite

50g potassium hydroxide

20g potassium bromide

0.5g
The volume was made up to 1000ml with water.

Next, Samples 1 to 6 were developed in the same manner as above in an unexposed state, and then the presence or absence of crater-shaped black foreign matter on the glass surface was examined using a stereoscopic microscope with a magnification of ×40. Furthermore, the tape releasability of the backing layers of Samples 1 to 6 was also examined. These results are shown in Table 2.

Table 2 Sample No. Emulsion layer tape Glass black Backing layer tape
Peelability *3 Foreign matter *4 Peelability *31 (comparative example) ×
10 pieces x 2 (comparative example)
△ 18 pieces
×3 (comparative example) 〇
13 pieces △4 (comparative example)
△ 0
〇5 (This invention) 〇
0 〇6 (present invention)
〇 0
〇

As is clear from Table 2,
Samples 5 and 6 according to the present invention had good tape removability after development treatment, crater-like black foreign matter, and tape removability of the backing layer without any problems.

Example 2 A copolymer consisting of ethyl methacrylate, methyl methacrylate, and methacrylic acid in a ratio of 3:3:4 was added to the emulsion of Sample-5 of Example 1. Sample 7 was prepared by coating a fluoride-treated glass support in the same manner as above. (Polymer loading amount: 60 mg/m2) This sample was evaluated in the same manner as in Example 1, and the adhesion between the emulsion layer and the backing layer was found to be good.

Example 3 [Preparation of emulsion] Solution A Water

9.7 liters sodium chloride

20g gelatin

105g

Solution B Water

3.8 liter gelatin

94g
sodium chloride

385g potassium bromide

450 g 0.01% aqueous solution of hexachloroiridate potassium salt 28 ml 0.0 of hexabromorhoridate potassium salt
1% aqueous solution 1.0ml

Solution C water

3.8 liters 0.1N nitric acid aqueous solution

90ml silver nitrate

170
0g

[0054] While stirring the solution A kept at 40°C using a mixer to create a uniform grain crystal habit as described in JP-A-57-92523 and JP-A-57-92524, pH 3 and pAg 7.7 were added. Add solution B and solution C simultaneously over 70 minutes while maintaining
After stirring for a minute, adjust the pH to 6 with an aqueous sodium carbonate solution.
．． 0, add 2 liters of 20% magnesium sulfate and 2.55 liters of a 5% aqueous solution of polynaphthalene sulfonic acid, flocculate the emulsion at 40°C, decant, and wash with water to remove excess aqueous solution. Remove salt.

Next, 3.7 liters of water is added to disperse the mixture, and 0.9 liters of a 20% aqueous magnesium sulfate solution is added again to remove excess salt from the aqueous solution. Add 3.7 liters of water and 141g of gelatin to it and
Disperse for 30 minutes at 0°C. As a result, particles containing 35 mol % of silver bromide, 65 mol % of silver chloride, and an average particle size of 0.27 μm are obtained.

A 1% aqueous solution of citric acid was added to this emulsion at 110%
After adding 140 ml of 5% potassium bromide aqueous solution and aging for 20 minutes, add 110 ml of 0.2% sodium thiosulfate aqueous solution and 0.2 ml of 0.2% sodium thiosulfate aqueous solution.
Add 140 ml of % chlorauric acid aqueous solution and heat at 60°C.
Matured to achieve maximum sensitivity. As a sensitizing dye, 1.8 g of Compound S shown below was added to perform spectral sensitization.

[0057]

[Formula 6] Compound S

Furthermore, 1-phenyl-5 is used as an antifoggant.
- 140 ml of a 0.5% aqueous solution of mercaptotetrazole and 2 ml of a 1% solution of 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene as a stabilizer.
Added liters.

To this emulsion, 1.1 g of the following compound I was added as a sensitizing dye, and 10% of hydroquinone was added as an antifoggant.
2 liters of solution, 170 liters of 5% aqueous solution of potassium bromide
ml, 370 ml of 20% saponin as a spreading agent, 110 ml of 1% citric acid aqueous solution,
140g of Compound J shown below, Compound D as a hardening agent
After adding, the silane coupling agent according to the present invention was added as shown in Table 3.
Added as shown.

[0060]

[C7]

[Preparation of backing coating solution] A backing coating solution similar to that in Example 1 was prepared. (Preparation of Samples) Each of the above-mentioned coating liquids was coated on both sides of a float glass support in the combinations shown in Table 3, and Sample 8 shown in Table 3 was applied.
and 9 were prepared. At that time, the emulsion layer has a gelatin content of 6.0
g/m2, and the silver amount was 4.1 g/m2.

The sample thus obtained was evaluated in exactly the same manner as in Example 1, except that it was processed at 20° C. for 3.5 minutes using the following developing solution 2 as a developing solution. The results are shown in Table 4.

(Developer-2) Hydroquinone

20g potassium sulfite

5g Sodium ethylenediaminetetraacetate
1g potassium carbonate

35g sodium carbonate

15g potassium bromide

3g

5-nitroindazole

4mg triethylene glycol

30g diethanolamine

20g formalin sodium bisulfite adduct
50g polyethylene glycol (average molecular weight 1500)
The volume was made up to 1 liter with 0.2 g water, and the pH was adjusted to 10.2 with sodium hydroxide.

Table 3 Sample No.
emulsion layer
Backing layer Fluoride Silane coupling agent Coated surface Fluoride Coated surface Treatment *1
Type Addition amount *2
Processing 8 (comparative example)
None (4) 6.2
Tin surface None Air surface 9 (invention)
Yes (4) 6.2
Tin side Yes Air side

[0066]

As is clear from Table 4, sample 9 of the present invention
No peeling occurs in either the emulsion layer or the backing layer,
It can be seen that the adhesiveness with the glass support is good.

Example 4 The same polymer as in Example 2 was added to the emulsion of Sample 9 of Example 3 and coated in the same manner as Sample 9 to prepare Sample 10. (Polymer loading amount: 90 mg/m2) This sample was used in Example 3.
Evaluation was carried out in the same manner as above, and both the emulsion layer and the backing layer had good adhesion to the glass support.

Example 5 [Preparation of emulsion coating solution] Rhodium chloride 2.0 was added during grain formation.
A silver chlorobromide gelatin emulsion containing 31 mol% of silver bromide was prepared by a back mixing method so as to contain 10-4 mol/1 mol of silver, and the emulsion was heated at 39°C.
, physical ripening was performed for 20 minutes. The emulsion thus prepared was desalted by a conventional method and gelatin was added to obtain a cubic emulsion with an average grain size of 0.2 μm.

The above emulsion was adjusted to pH=6.0, and 850 mg of potassium iodide and 28 mg of potassium iodide were added per mole of silver halide.
After adding 0 mg of potassium bromide, 150 mg of formalin per mole of silver halide was added and aged 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. In addition,
Reduction fog was caused by aging at 60° C. for 110 minutes. After aging, adjust the pH to 6.5 with citric acid.

The following compounds [K], [L], [M], [N], [O] are added to the fogged emulsion as additives.
], [P], [Q], potassium bromide, triethyltetramine, saponin, and the following compound [R] as a hardening agent and the silane coupling agent (4) according to the present invention were added.

[0072]

[Chemical formula 8]

[0073]

[Chemical formula 9]

The backing liquid was prepared in the same manner as in Example 1. [Preparation of photosensitive material sample] 0.05% hydrogen fluoride and 2 sulfuric acid
Sample 11 was prepared by immersing a float glass support in an aqueous solution containing 10% of the total weight for 2 minutes, washing it with water, applying the above emulsion coating liquid to the tin surface, and further applying a backing liquid to the air surface. (Amount of silver coating 3.6g/m2, amount of gelatin coating 4.
7g/m2)

When the sample thus obtained was evaluated in the same manner as in Example 3, both the emulsion layer and the backing layer had good adhesion to the glass support.

[0076]

Effects of the Invention The present invention improves adhesion with the emulsion layer by coating a silver halide emulsion layer containing a silane coupling agent on the tin side of a float glass support whose surface has been treated with fluoride. Further, by providing an antihalation layer on the air surface of the float glass support whose surface has been treated with a fluoride, the adhesion between the air surface and the antihalation layer is improved.

Claims (1)

[Claims] Claim 1: A silver halide photographic material having a silver halide emulsion layer on the tin side of a float glass substrate surface-treated with fluoride, which contains a silane coupling agent in a layer constituting the emulsion layer. and an antihalation layer containing a light-absorbing dye on the air side of the float glass support.