JPH05289218A - Silver halide photographic dry plate photosensitive material - Google Patents

Abstract

PURPOSE:To provide a silver halide photographic dry plate photosensitive material which has viscoelasticity and defect of which is easily without affecting photographic performance. CONSTITUTION:This silver halide photographic dry plate photosensitive material has at least one photosensitive silver halide emulsion layer on one side of a glass supporting body. Also, the photosensitive material contains >=800mg/m<2> latex polymer in the same side of body as the silver halide emulsion layer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic dry plate photographic material, and more particularly to a silver halide photographic dry plate photographic material capable of easily correcting defects.

[0002]

BACKGROUND OF THE INVENTION Photomasks for making electronic components such as printed boards and lead frames are printed with fine patterns. If foreign matter (dust, glass chips, etc.) adheres to the dry plate, defects such as blackening due to pressure and pattern defects or scratches due to the glass chips or the like in the image area will cause pattern noise. The same applies to scratches in handling.

As one of the image correction methods, it is well known that the gelatin film at the defective portion is pulled with tweezers or the like to cover the defective portion, but the gelatin film after hardening has insufficient viscoelasticity and is cut. It was easy to do and required a fairly high level of skill.

[0004]

SUMMARY OF THE INVENTION In view of the above problems, it is an object of the present invention to provide a silver halide photographic dry plate light-sensitive material having viscoelasticity which does not affect photographic performance and is easy to correct defects.

[0005]

The above object of the present invention is to provide a silver halide photographic plate light-sensitive material having at least one light-sensitive silver halide emulsion layer on one side on a glass support, on the same side as the silver halide emulsion layer. Latex polymer to 800 mg / m ²
This has been achieved by a silver halide photographic dry plate light-sensitive material characterized by containing the above.

The present invention will be described in detail below.

The latex polymer used in the present invention is
Those containing a (meth) acrylic acid-based polymer unit are preferable. Examples of the (meth) acrylic acid-based polymer include a (meth) acrylic acid copolymer, a (meth) acrylic acid ester homopolymer, and a (meth) acrylic acid ester copolymer. Specifically, alkyl acrylate homopolymers, alkyl acrylates and alkyl methacrylates polymerized together, alkyl methacrylate homopolymers, alkyl acrylates, alkyl methacrylates, acrylates, methacrylates and other ethylenically unsaturated polymerizable compounds. those having one or more than one -CH = C <, preferably be mentioned one or a water-insoluble addition polymer, such as one or more CH ₂ = C <those obtained by polymerizing a material having a it can.

Specific examples of the above-mentioned (meth) acrylic acid type polymer include, for example, copolymers of acrylate and vinylidene chloride, copolymers of methacrylate and vinylidene chloride, copolymers of acrylate and vinyl ester, and copolymers of methacrylate and vinyl ester. Examples thereof include a copolymer of at least one compound selected from the copolymers and a compound of at least one compound selected from acrylic acid, methacrylic acid, and itaconic acid, and these copolymers are preferable.

Specific examples of acrylates and methacrylates include ethyl acrylate, n-butyl acrylate, n-octyl acrylate, n-dodecyl acrylate, ethyl methacrylate, n-butyl methacrylate, n-octyl methacrylate and n-dodecyl methacrylate. Etc. Specific examples of the vinyl ester include vinyl butyrate, vinyl propionate, vinyl acetate, vinyl laurate and the like. The molecular weight of the copolymer is practically preferably about 500 to 500,000. Specific examples of such homopolymers or copolymers are shown below as L-1 to L.
-13, but is not limited to these homopolymers or copolymers.

[0010]

[Chemical 1]

[0011]

[Chemical 2]

[0012]

[Chemical 3]

In the above L-1 to L-13, x,
y and z represent the mol% of each monomer component, and M represents the average molecular weight (in the present specification, the average molecular weight refers to the number average molecular weight).

Generally, as the (meth) acrylic acid-based polymer, at least 65%, preferably 75 to 95% by weight of alkyl acrylate, alkyl methacrylate (eg, ethyl acrylate, methyl acrylate, butyl acrylate, ethyl acrylate, octyl methacrylate, etc.) It is desirable to use a polymer having
The polymers most useful in the practice of the present invention are generally those having an average molecular weight of from about 500 to about 500,000 and a particle size in the dispersion of generally 1 μm or less, as described above.

The above-mentioned (meth) acrylic acid-based polymer is insoluble in water but can be easily dispersed in water, and the above-mentioned (meth) acrylic acid-based polymer is a suitable silver halide peptizer such as gelatin. It can be used alone or mixed with other photographic binders.

The amount of the latex polymer contained in the silver halide photographic light-sensitive material of the present invention is m ^{2 in} terms of solid content.
It is preferable to add 800 mg to 10 g, and particularly preferable to add 1 g to 5 g.

The silver halide emulsion used in the light-sensitive material of the present invention may be obtained by any of the acid method, the neutral method and the ammonia method, and the grain size is preferably 0.2 μm or more and 0.5 μm or less. In the silver halide grains used in the emulsion of the present invention, a water-soluble rhodium salt and a water-soluble iridium salt are added in the process of forming the grains so as to be incorporated inside the grains and / or on the grain surfaces. The addition amount is 10 ^-6 per mol of silver halide.
~ ^10-9 mol is preferred.

The silver halide grain may be one having a uniform silver halide composition distribution within the grain, or a core / shell grain having a different silver halide composition between the inside of the grain and the surface layer, and a latent image May be particles mainly formed on the surface, or particles mainly formed inside the particles.

The silver halide grains according to the present invention may have any shape. One preferred example is
It is a cube having a {100} plane as a crystal surface. or,
U.S. Pat.Nos. 4,183,756 and 4,225,666, JP-A-55-2658
No. 9, Japanese Patent Publication No. 55-42737, etc., and The Journal of Photographic Science (J.Photgr.S)
ci). 21 . By the method described in the literature such as 39 (1973), particles having an octahedron, a tetradecahedral shape, a dodecahedron shape, etc. can be prepared and used. Further, grains having twin planes may be used.

The silver halide grain according to the present invention may be a grain having a single shape, or may be a mixture of grains having various shapes.

Any grain size distribution may be used, an emulsion having a wide grain size distribution (referred to as polydisperse emulsion) may be used, or an emulsion having a narrow grain size distribution (referred to as monodisperse emulsion). .) May be used alone or in combination of several kinds. Further, a polydisperse emulsion and a monodisperse emulsion may be mixed and used.

As the silver halide emulsion, two or more kinds of silver halide emulsions formed separately may be mixed and used.

In the present invention, a monodisperse emulsion is preferred.
As the monodisperse silver halide grains in the monodisperse emulsion, when the weight of silver halide contained in the grain size range of ± 20% around the average grain size r is 60% or more of the total weight of silver halide grains, Some are preferable, particularly preferably 70% or more, further preferably 80% or more.

Here, the average particle diameter r is the particle diameter ri when the product ni × ri ³ of the frequency ni and ri ³ of the particles having the particle diameter ri becomes maximum.
Is defined.

(Three significant digits and the least significant digit are rounded off.) The grain size referred to here is the diameter of spherical silver halide grains, or the grain size of grains other than spherical grains. It is the diameter when the projected image is converted into a circular image of the peripheral area.

The particle size can be obtained, for example, by magnifying the particles with an electron microscope from 10,000 times to 50,000 times and measuring the particle diameter on the print or the area at the time of projection. (The number of measured grains is indiscriminately 1000 or more.) A particularly preferred highly monodisperse emulsion of the present invention has a monodispersity degree defined by grain size standard deviation / mean grain size × 100 = monodispersity degree. It is 20 or less, more preferably 15 or less.

Here, the average particle size and the particle size standard deviation are obtained from ri defined above. Monodisperse emulsion is disclosed in JP-A-54-
It can be obtained by referring to 48521, 58-49938 and 60-122935.

The light-sensitive silver halide emulsion can be used as it is as a so-called unripened (Primitive) emulsion without chemical sensitization, but it is usually chemically sensitized. For chemical sensitization, Glafkides or Zelikman's book, or
H. Frieser edited by Die Grundlagen der Photographischen Prozesse mit
Silberhalogeniden ； Akademicche Verlagsgesellschaf
t; 1968).

That is, a sulfur sensitizing method using a compound containing sulfur capable of reacting with silver ions or active gelatin, a reduction sensitizing method using a reducing substance, a gold or other noble metal compound can be used. As the sulfur sensitizer, thiosulfates, thioureas, thiazoles, rhodanines, and other compounds can be used, and specific examples thereof include U.S. Pat.
944, 2,410,689, 2,278,947, 2,728,668
No. 3,656,955. Examples of the reduction sensitizers include primary tin salts, amines, hydrazine derivatives, formamidisulfinic acid, and silane compounds, and specific examples thereof are U.S. Patents 2,487,850 and 2,41.
9,974, 2,518,698, 2,983,609, 2,983,610
No. 2,694,637. For sensitizing a noble metal, in addition to a gold complex salt, a complex salt of a metal of Group VII of the periodic table such as platinum, iridium and palladium can be used, and specific examples thereof are U.S. Patents 2,399,083, 2,448,060 and British Patent 618,061. No. etc.

The conditions such as pH, pAg and temperature during chemical sensitization are not particularly limited, but the pH value is 4-9, especially 5-8.
Is preferable, and it is preferable to keep the pAg value at 5 to 11, and especially at 7 to 9. The temperature should be 40 to 90 ℃, especially 45 to 75 ℃.
C is preferred.

In the photographic emulsion used in the present invention, in addition to the above-mentioned sulfur sensitization, gold / sulfur sensitization, a reduction sensitization method using a reducing substance: a noble metal sensitization method using a noble metal compound can be used in combination. ..

As the photosensitive emulsion, the above emulsions may be used alone, or two or more kinds of emulsions may be mixed.

In the practice of the present invention, after completion of the chemical sensitization as described above, for example, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene, 5-mercapto-1-phenyl Various stabilizers such as tetrazole and 2-mercaptobenzothiazole can be used. If necessary, a silver halide solvent such as thioether, or a crystal habit controlling agent such as a mercapto group-containing compound or a sensitizing dye may be used.

In the emulsion of the present invention, unnecessary soluble salts may be removed after the completion of the growth of silver halide grains, or may be contained. When removing the salts,
It can be carried out based on the method described in Research Disclosure 17643.

Various compounds can be added to the above photographic emulsion in order to prevent the deterioration of sensitivity and the occurrence of fog during the manufacturing process, storage or processing of the silver halide photographic light-sensitive material. That is, azoles such as benzothiazolium salt,
Nitroindazoles, triazoles, benzotriazoles, benzimidazoles (particularly nitro- or halogen-substituted), heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzimidazoles, mercaptothiazoles, mercaptotetrazole (especially 1- Phenyl-5-mercaptotetrazole),
Mercaptopyridines, the above heterocycles having a water-soluble group such as a carboxyl group or a sulfone group, mercapto compounds, thioketo compounds such as oxazoline thione, azaindenes such as tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a , 7) Tetraazaindenes), benzenethiosulfonic acids, benzenesulfinic acid, and many other compounds known as stabilizers can be added. An example of a compound that can be used is K. Mees, The Theory of the Photographic Process.
ry of the Photographic Process, 3rd edition, 1966). For more detailed specific examples of these and other methods of use, reference can be made to the descriptions in US Pat. Nos. 3,954,474, 3,982,947, 4,021,248 and JP-B-52-28660.

The silver halide photographic light-sensitive material of the present invention has US Pat. Nos. 3,411,911 and 3,411,912 in the photographic constituent layers.
Alkyl acrylate-based latex described in JP-B No. 45-5331, etc.

The silver halide photographic light-sensitive material of the present invention may contain the following various additives. As a thickener or a plasticizer, for example, U.S. Pat.
Substances described in each specification of 588,143, for example, styrene-sodium maleate copolymer, dextran sulfate, etc., as hardeners, aldehyde-based, epoxy-based, ethyleneimine-based, active halogen-based, vinyl sulfone-based , Isocyanate-based, sulfonate-based, carbodiimide-based, mucochloric acid-based, various hardeners such as acyloyl-based, as the ultraviolet absorber, for example, U.S. Pat.
Compounds described in the specifications such as 921 and British Patent 1,309,349, particularly 2- (2'-hydroxy-5-tertiarybutylphenyl) benzotriazole, 2- (2'-hydroxy-
3 ', 5'-di-tertiarybutylphenyl) benzotriazole, 2- (2-hydroxy-3'-tertiarybutyl-5'-butylphenyl) -5-chlorobenzotriazole, 2- (2'
-Hydroxy-3 ', 5'-di-3-tert-butylphenyl) -5
-Chlorobenzotriazole and the like can be mentioned.
Further, coating aids, emulsifiers, agents for improving the permeability to processing solutions, defoamers, or surfactants used for controlling various physical properties of light-sensitive materials include British Patents 548,532 and 1,216,389. No., U.S. Patent No. 2,026,202,
No. 3,514,293, Japanese Patent Publication No. 44-26580, No. 43-17922,
43-17926, 43-3166, 48-20785, French Patent 202,588, Belgian Patent 773,459, JP-A-48-10.
Although anionic, cationic, nonionic or amphoteric compounds described in 1118 etc. can be used,
Of these, anionic surfactants having a sulfone group, such as succinate sulfonates and alkylbenzene sulfonates, are particularly preferable. In addition, as an antistatic agent, Japanese Patent Publication No. Sho 24-24159, Japanese Unexamined Patent Publication No. Sho 48-89979, and U.S. Pat.
2,882,157, 2,972,535, JP-A-48-20785, 4
8-43130, 48-90391, JP-B-46-24159, 46
-39312, 48-43809 and JP-A-47-33627. In the production method of the present invention, the pH of the coating liquid is preferably in the range of 5.3 to 7.5. In the case of multi-layer coating, it is preferable that the pH of the coating liquid prepared by mixing the coating liquids of the respective layers in the coating amount ratio is in the range of 5.3 to 7.5. If the pH is less than 5.3, the progress of dura is slow, which is not preferable, and if the pH is more than 7.5, it is not preferable that the photographic performance is adversely affected.

In the light-sensitive material of the present invention, a slip agent, for example, a higher aliphatic higher alcohol ester described in US Pat. Nos. 2,588,756 and 3,121,060, and US Pat.
Casein described in 295,979, higher aliphatic calcium salts described in British Patent 1,263,722, British Patent 1,313,384,
The silicon compounds described in US Pat. Nos. 3,042,522 and 3,489,567 may be included. Liquid paraffin dispersions and the like can also be used for this purpose.

Various additives can be further used in the light-sensitive material of the present invention depending on the purpose. These additives are described in more detail in Research Disclosure No. 176.
Volume Item17643 (December 1978) and Volume 187 Item18716 (1
(November 979), and the relevant parts are summarized in the table below.

Additives RD17643 RD18716 1. Chemical sensitizer, page 23, page 648, right column 2. Sensitivity enhancer, same as above 3. Spectral sensitizer / supersensitizer, page 23-24, page 648, right column-649 Page right column 4. Whitening agent page 24 5. Antifoggants and stabilizers 24 to 25 pages 649 right column 6. Light absorbers, filters pages 25 to 26 649 Right column to 650 left column Dyes, UV absorbers 7 Anti-staining agent Page 25 Right column Page 650 Left-right column 8. Dye image stabilizer Page 25 9. Hardener 26 Page 651 Left column 10. Binder Page 26 Same as above 11. Plasticizers / Lubricants Page 27 650 Right Column 12. Coating Aids / Surfactants, pages 26 to 27, ibid., 13. Antistatic Agent, p. 27, ibid. Photographic processing of the silver halide photographic light-sensitive material according to the present invention is
Various methods can be used without particular limitation. The processing temperature is
Usually, it is selected between 18 ° C and 50 ° C, but the temperature may be lower than 18 ° C or higher than 50 ° C.

The developing agent used in the black-and-white developing solution used in the present invention is likely to have good performance, and thus dihydroxybenzenes (for example, hydroquinone), 3-pyrazolidones (for example, 1-phenyl-3-pyrazolidone), aminophenol. The compounds (for example, N-methyl-p-aminophenol) and the like can be used alone or in combination.

The glass support used in the present invention is not particularly limited in glass composition, but soda lime glass, soda lime aluminum glass and the like are preferable.

It is also possible to use a float glass produced by allowing molten glass to cool on a molten tin bath.

In the light-sensitive material of the present invention, at least one silver halide emulsion layer is provided on a glass support, and in addition to the layer, an appropriate layer is provided, for example, a protective layer is provided on the emulsion layer. You can

In the light-sensitive material of the present invention, a backing layer containing a light absorbing dye can be provided on the surface opposite to the silver halide emulsion layer. The light absorbing dye can be selected from any dyes.

In the photographic processing of the silver halide photographic light-sensitive material of the present invention, it is also possible to perform processing with a developing solution containing an imidazole as a silver halide solvent. It is also possible to perform processing with a developing solution containing a silver halide solvent and an additive such as indazole or triazole. The developer generally contains various other preservatives, alkali agents, pH buffers, antifoggants and the like, and further contains a solubilizing agent, a toning agent, if necessary.
It may contain a development accelerator, a surfactant, a defoaming agent, a water softener, a film hardener, a viscosity imparting agent and the like.

Further, so-called "lith type" development processing can be carried out. As a special form of development processing, a method may be used in which a developing agent is contained in a light-sensitive material, for example, in an emulsion layer, and the light-sensitive material is treated with an alkaline aqueous solution for development. Research on hydrophobic developing agents. It can be incorporated in the emulsion layer by the method described in Disclosure No. 169 et al. Such a development process may be combined with a silver salt stabilization process using a thiocyanate.

As the fixing liquid, those having a generally used composition can be used. The fixer may contain a water-soluble aluminum salt as a hardening agent.

The exposure to the photographic emulsion used in the present invention depends on the state of chemical sensitization, purpose of use, etc., but it is different from tungsten, fluorescent lamp, arc lamp, mercury lamp, xenon sunlight, xenon flash, cathode ray tube flying spot, laser. Various light sources such as light, electron beams, X-rays, and fluorescent screens during X-ray imaging can be used as appropriate.

With respect to the exposure time, in addition to the normal exposure of ^1/100 to 100 seconds, a short exposure of 1/10 ^-4 to 1/10 ^-9 seconds can be applied to xenon flash, cathode ray tube and laser light.

[0051]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto.

Example 1 (Preparation of coating solution for emulsion layer) Solution A water 9.7 l Sodium chloride 20 g Gelatin 105 g Solution B water 3.8 l Sodium chloride 409 g Gelatin 94 g Potassium bromide 360 g 0.01% aqueous solution of potassium hexachloroiridate 28 ml hexa 0.001% aqueous solution of potassium bromorhodate salt 14 ml solution C water 3.8 l silver nitrate 1,700 g In solution A kept at 38 ° C., while maintaining pH 3.5 and pAg 8.0, both solution B and solution C were functionally To the mixture for 20 minutes and stirring for 10 minutes, adjust the pH to 5.8 with an aqueous solution of sodium carbonate, add 1.7 l of 20% magnesium sulfate aqueous solution and 5% of polynaphthalene sulfonic acid.
2.55 l of an aqueous solution is added, the emulsion is flocculated at 35 ° C., decanted and washed with water to remove excess salt from the aqueous solution. Then, 3.7 l of water is added thereto to disperse the same, and 0.9 l of a 20% aqueous magnesium sulfate solution is again added to similarly remove excess salt from the aqueous solution. 3.7 l of water and 141 g of gelatin are added thereto and dispersed at 55 ° C. for 30 minutes. This gives cubic grains having a silver bromide content of 30 mol%, a silver chloride content of 70 mol%, an average of 0.23 μm and a monodispersity of 9. After adjusting the pH to 5.5 and pAg7 by adding 12 ml of 1% citric acid aqueous solution and 60 ml of 5% potassium bromide aqueous solution, add 85 ml of 0.1% sodium thiosulfate aqueous solution and age at 50 ° C for maximum sensitivity. I chose

Then, 10 g of the compound (a) was added.

(Preparation of emulsion layer) Silver halide emulsion 0.353
The following additives are added per mole.

Sensitizing dye [A] 50 mg Sensitizing dye [B] 30 mg Compound (b) 30 mg Compound (c) 40 mg Potassium bromide 100 mg Citric acid 50 mg Compound (d) 300 mg Polymer latex shown in Table 1 (e) 200 mg Compound (f) 30 mg Spreading agent Saponin manufactured by Merck Co., Ltd. 2600 mg (Preparation of backing coating solution) To a mixed solvent of methanol and ethanol, compound D having the following structure was added as a binder, and exemplified compounds 1 to 5 were added as light absorbing dyes.

(Preparation of Sample) The above coating solution and the like were applied on both sides of a glass support (hereinafter abbreviated as float glass) whose glass surface was surface-treated with a stannic chloride solution to prepare a sample of a photosensitive material. ..

At this time, the emulsion layer was coated so that the amount of gelatin was 5 g / m ² and the amount of silver was 4.2 g / m ² .

[0058]

[Chemical 4]

[0059]

[Chemical 5]

(Defect Correction and Evaluation Method Thereof) The sample thus prepared is seasoned at 50 ° C. and 80% relative humidity for 12 hours to artificially form defects (scratches) of 30 to 50 μm size. Next, after exposing this sample using a line and space pattern of 100 microns, Konica Developer C
A defective mask is prepared by performing development processing at 20 ° C. for 2 minutes and 15 seconds with DL-271 and Konica fixer CFL-811.

After swelling the periphery of the defect (scratch) sufficiently with pure water under a microscope with a magnification of 40 times, the gelatin film is pulled with sharp tweezers to correct the defect. The defective portion correction success rate at this time was used as the evaluation method.

The results are shown in Table 1.

[0063]

[Table 1]

From the results shown in Table 1, it is understood that according to the present invention, a silver halide photographic dry plate light-sensitive material having viscoelasticity which is easy to correct defects can be provided.

[0065]

According to the present invention, the photographic performance is not affected,
It is possible to provide a silver halide photographic dry plate light-sensitive material having viscoelasticity that is easy to correct defects.

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on one side of a glass support, wherein 800 mg / m of latex polymer is provided on the same side as the silver halide emulsion layer. ^A silver halide photographic dry plate light-sensitive material containing ^two or more.