US3707379A - Process for the formation of photographic images - Google Patents

Process for the formation of photographic images Download PDF

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Publication number
US3707379A
US3707379A US825347A US3707379DA US3707379A US 3707379 A US3707379 A US 3707379A US 825347 A US825347 A US 825347A US 3707379D A US3707379D A US 3707379DA US 3707379 A US3707379 A US 3707379A
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Prior art keywords
image
oxopyrazolidine
developing
reducing agent
group
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US825347A
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Yoshihide Hayakawa
Yasuhiro Noguchi
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/0285—Silver salts, e.g. a latent silver salt image

Definitions

  • a polymer image is formed on a photographic film on those areas which have been exposed and developed, the image proportional to the amount of exposure.
  • the polymer image may then be dyed.
  • the image is developed from a latent image in a photographic emulsion by developing the emulsion, in the presence of a vinyl or vinylidene monomer, with a reducing agent capable of developing the silver halide emulsion layer and at the same time initiating polymerization, said agent selected from resorcinols, m-aminophenols, naphthols, pyrazoline-S-ones and phenols, and a reducing agent of the general formula wherein A represents an oxygen atom or an imino group, B represents a phenyl group, R R and R each represents a hydrogen atom or an alkyl group having 1-6 carbon atoms, and R represents a hydrogen atom, an alkyl group having 1-6 carbon atoms, an ary
  • the present invention relates to a process for the formation of photographic images and more particularly to a process for forming a polymeric image on a photographic film, the polymeric image corresponding to the latent image formed by exposure of the photographic emulsion layer.
  • reducing agents capable of initiating polymerization there are illustrated resorcinol, m-aminophenols, derivatives thereof, naphthol derivatives, 2-pyrazoline-5- ones, 3-pyrazoline-5-ones, and phenols.
  • these reducing agents generally have a weaker reducing power than developing agents commonly employed in photographic processings, it takes a considerably longer "ice period of time to finish the development. Consequently, photographic sensitivity is lowered.
  • An object of the present invention is to provide an improved process for forming a polymer image corresponding to a latent image by developing a silver halide photographic emulsion layer having the latent image with a reducing agent such as, a resorcinol, a m-aminophenol, a naphthol, a pyrazoline-S-one, and a phenol, capable of initiating the polymerization of a vinyl or vinyldiene compound and reducing at the same time the silver halide in the photographic emulsion layer, in the presence of a vinyl compound or a vinylidene compound, wherein the developing speed is increased and the sensitivity of the photographic emulsion is also increased.
  • a reducing agent such as, a resorcinol, a m-aminophenol, a naphthol, a pyrazoline-S-one, and a phenol
  • the object of the present invention can be attained by incorporating into the developing solution for a silver halide emulsion layer containing therein a reducing agent capable of initiating the polymerization of a vinyl or vinylidene compound in the presence of the vinyl or vinylidene compound, a 3-oxopyrazolidine or a 3-irninopyrazoline represented by the general Formula I wherein A represents an oxygen atom or an imino group; B represents a phenyl group or a substituted phenyl group; R R and R each represents a hydrogen atom or an alkyl group having l-6 carbon atoms; and R represents a hydrogen atom, an alkyl group having 1-6 carbon atoms, an aryl group, or a carboxyl group.
  • the compound of Formula I may also be incorporated into the processing solution for the silver halide photographic emulsion layer, thereafter developing the emulsion layer with the abovementioned reducing agent in the presence of the vinyl or vinylidene compound.
  • the compound represented by the above-mentioned general formula may be the tautomer as shown below
  • reducing agents capable of reducing silver halide in a silver halide emulsion and at the same time initiating the polymerization of a vinyl compound or a vinylidene compound there may be employed in the present invention the aforesaid resorcinols, m-aminophenols, naphthols,
  • 2-pyrazoline-5-ones 3-pyrazoline-5-ones, and phenols.
  • the typical examples of these compounds are resorcinol, m-aminophenol, 1-amino-8-naphthol-3,6-disulfonic acid, 3, 4-dimethyl-S-pyrazolone, o-xylenol, and the like.
  • the 3-iminopyrazolidines represented by general Formula I are also effectively used as usual photographic developing agents and are disclosed in British Pat. No. 757,- 840 and German Pat. No. 870,418.
  • Typical examples of the 3-iminopyrazolidines are 1-phenyl-3-iminopyrazolidine, l,5-diphenyl-3-iminopyrazolidine, l-p-hydroxyphenyl-3 iminopyrazolidine, 1 p-methoxyphenyl-3-iminopyrazolidine, and the like.
  • the combination in the present invention is different from the conventional combination in the kind of reducing agent as well as purposes.
  • the purpose of employing both reducing agents (developing agents) is to reduce silver halide into silver and the synergistic property is obtained in the speed of the formation of the silver.
  • the reducing agent serves the dual function of reducing a silver halide to silver and at the same time initiating the radical polymerization of a vinyl compound or a vinylidene compound
  • the pyrazolidine derivative represented by general Formula I reduces a silver halide to silver but does not initiate polymerization.
  • 1-phenyl-3-oxopyrazolidine exhibits a strong developing action but has no function of initiating the polymerization of the monomer.
  • the advantage of the present invention lies in the fact that by using the reducing agent having a strong developing power together with the reducing agent capable of initiating the polymerization of the monomer but having a weak reducing power, the initiation of the polymerization by the latter reducing agent can be conducted rapidly, while also obtaining a high sensitivity for the photographic silver halide emulsion layer.
  • the developing mechanism particularly the initial mechanism by the silver halide photographic emulsion in the process of this invention has not been sufiiciently claritied. It i et c ear how th nt zina en in th s invent on acts effectively but the following two mechanisms are considered:
  • the developing agent of the structure of Formula I having a high developing activity, acts first on the developing nuclei to increase the size thereof, whereby the developing action of the reducing agent having a function of initiating polymerization and a weak developing activity is facilitated.
  • the polymerization reaction is started by oxidizing the reducing agent having a function of initiating polymerization with the oxidation product of the developing agent having the structure (I).
  • the oxidation reduction potential of the developing agent having the structure (I) shown above is lower (stronger in reducing property) than that of the reducing agent having the function of initiating polymerization by 200-300 m.v., if the concentration ratio of the latter to the former is not sufliciently high, neither the reduction of silver halide nor the reduction of the oxidation product of the former becomes possible. This is the reason why the amount of the developer having the structure (I) must be less than the amount of the reducing agent having the function of initiating polymerization.
  • the ratio is preferably less than ,5 in mole ratio preferably to M10390 in mole ratio.
  • the inventors have previously reported that the same effect as in the present invention can be obtained by employing p-amino-phenol, pyrocatechin, amidol or the like together with the reducing agent having the function of initiating polymerization.
  • the photographic emulsion, light source, etc. used in the present invention are those generally employed in conventional developing procedures.
  • vinyl compound or the vinylidene compound used in the present invention there are illus trated acrylamide, acrylonitrile, N-hydroxymethyl acrylamide, methacrylic acid, acrylic acid, calcium acrylate, sodium acrylate, methacrylamide, methyl methacrylate, methyl acrylate, ethyl acrylate, vinylpyrrolidone, vinyl methyl ether, vinyl butyl ether, vinyl isopropyl ether, vinyl isobutyl ether, vinyl butyrate, 2-vinyl-pyridine, 4-vinylpyridine, Z-methyl-N-vinylimidazole, potassium vinylbenzene sulfonate, vinylcarbazole, N,N'-methylenebis acrylamide, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, divinyl ether, divinyl benzene and the like.
  • sulfite ions are present i th y em whe th p ymerization of the above mono mer is conducted according to the process of this invention. Moreover, by dyeing the polymer image formed by the process of this invention, a color image can be prepared.
  • EXAMPLE 1 A photographic light-sensitive film having a photographic gelatino silver halide emulsion was light-exposed and then developed with 8-amino-1-naphthol-3,6-disulfonic acid and l-phenyl-3-oxopyrazolidine to conduct the polymerization of methacrylic acid.
  • the photographic light-sensitive film was prepared as follows: After applying under coatings to both surfaces of a polyethylene terephthalate film, an antihalation layer was formed on the one surface thereof and the other surface thereof was coated with a fine particle-type gelatino silver halide emulsion containing about 0.7 mole of chlorine, about 0.3 mole of bromine, about 0.001 mole of iodine and about 100 g. of gelatin per mole of silver, said silver halide emulsion having further been mixed with a merocyanine dye having a sensitivity maximum at 550 m as a sensitizing dye, mucochloric acid in an amount of about 1.5 g. per 100 g.
  • the photographic light-sensitive film thus prepared was a type usually employed for making line and half-tone images for graphic arts.
  • each sample was not subjected to dyeing while the other part, subjected to the dyeing and bleaching procedure, formed a dyed polymer image.
  • Each image 6 was measured for optical density through a green filter, the results of which are shown in FIG. 1 and FIG. 2.
  • FIG. 1 shows a characteristic curve obtained from the silver image.
  • FIG. 2 shows a characteristic curve obtained from the dyed image and corresponds to the amount of the polymer formed.
  • No. 1 stands for sample number 1
  • No. 2 for sample number 2
  • No. 3 for sample number 3.
  • sample 3 containing 1-amino-8-naphthol-3,6-disulfonic acid and 1-phenyl-3-oxopyrazolidine has a density equal almost to the sum of the density of sample 1 and sample 2.
  • the exposure amount in sample 3 may be about 0.6 (as logarithm of the exposure amount) lower than the exposure amount in sample 2, which shows the effective sensitivity of sample 3 was increased to about four times that of sample 2.
  • EXAMPLE 2 The same kind of the photographic light sensitive film as in Example 1 was exposed as in that example and then developed in a solution having the following composition:
  • the sample After developing as above for a period of time as shown in Column A of Table I, the sample was subjected to fixing, washing, bleaching, washing and drying.
  • the step number of least exposure susceptible to dyeing at which the dye image was observed was measured visually, the results of which are shown in Column B of Table I.
  • the density of dye image of each sample was measured, and the results compared.
  • Table I the step number used in the above measurement is shown in Column C, the density of dye image at the step is shown in Column D, the density of the background fog is shown in Column E, and the true density of dye image (i.e., D-E) is shown in Column F.
  • the value in Column F corresponds to the amount of the polymer formed caused by the specific amount of exposure given to the emulsion layer.
  • the step number by which the formation of dye image was observed was increased and at the same time the F value was increased. This shows that the formation rate of polymer was increased and the effective sensitivity was also increased.
  • EXAMPLE 3 The photographic light-sensitive film as in Example 1 was exposed, pre-treated in an aqueous alkaline solution of 1-phenyl-3-oxopyrazolidine, and then developed by using resorcinol to conduct polymerization.
  • Example 2 After exposing the sample for 10 seconds at 50 luxes as in Example 1, the sample was pretreated in an aqueous solution containing 0.1 g./liter of 1-phenyl-3-oxopyrazolidine, the pH of which had been adjusted to 10.5 by adding sodium carbonate, at 30 C. for a period of time shown in Table II, washed thrice for 15 seconds each with distilled water, and then immersed in a solution having the following composition for 30 minutes at 30 C. to conduct development and polymerization:
  • the oxopyrazolidine processing solution contained no methacrylic acid monomer and hence by the treatment by the oxopyrazolidine processing solution, no polymer was formed and hence a dye image was of course not obtained. Therefore, it is clear that the pretreatment by oxopyrazolidine promoted the development and polymerization by the resorcinol-methacrylate system.
  • EXAMPLE 4 The same procedure as in Example 3 was repeated using a silver iodobromide emulsion.
  • the other surface was coated with a fine particle-type gelatino silver halide emulsion containing 0.012 mole of iodine, 0.988 mole of bromine, and about 204 g. of gelatin per 1 mole of silver, which had been sensitized by a rhodan complex salt of mono-valent gold and mixed with 0.3 g. of 6-methyl-4- hydroxy-1,3,32,7-tetraazaindene per mole of silver as a stabilizer, about 0.7 g. of mucochloric acid per g.
  • gelatin as a hardening agent, and also a suitable surface active agent so that 60 mg. of silver was contained in the emulsion layer of 100 cm. Further, a protective gelatin layer of about 0.8 micron in thickness was formed on the emulsion layer.
  • a type of photographic light sensitive film is usually used for making line images by photoengraving process and continuous positive images of soft tone.
  • Example 2 After exposing the film sample thus prepared for 1 second at 50 luxes as in Example 1, the sample was pretreated in an aqueous solution of 1-phenyl-3-oxopyrazolidine as in Example 3, washed with water thrice each for 15 seconds with distilled water, and then immersed for 15 minutes at 30 C. in a solution having the following composition to conduct the development and polymerization simultaneously:
  • A represents an oxygen atom or an imino group
  • B represents a phenyl group or a substituted phenyl group
  • R R and R each represents a hydrogen atom, or an alkyl group having 1-6 carbon atoms
  • R represents a hydrogen atom, an alkyl group having 1-6 carbon atoms, an aryl group or a carboxyl group.
  • said reducing agent is a member selected from the group consisting of a resorcinol, a m-aminophenol, a naphthol, a pyrazoline-5- one, and a phenol.
  • said reducing agent is a member selected from the group consisting of resorcinol, N,N-dimethylmethaminophenol, 3,4 dimethyl-S- pyrazolone, and o-xylenol.
  • said vinyl or vinylidene compound is a member selected from the group consisting of acrylamide, acrylonitrile, N-hydroxymethylacrylamide, methacrylic acid, acrylic acid, calcium acryate, sodium acrylate, methacrylamide, methylmethacrylate, methylacrylate, ethylacrylate, vinylpyrrolidone, vinylmethyl ether, vinyl butyl ether, vinyl isopropyl ether, vinyl isobutyl ether, vinyl butyrate, 2-vinyl-pyridine, 4- vinylpyridine, Z-methyl-N-vinylimidazole, potassium vinyl benzene sulfonate, vinylcarbazole, N,N-methylene-bis acrylamide, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, divinyl ether, and divinyl benzene.
  • said pyrazolidine compound is a member selected from the group consisting of 1-pheno1-3-oxopyrazolidine, l-phenol-4-methyl-3- oxopyrazolidine, 1-phenol-3-oxopyrazolidine-S-carboxylic acid, 1 p-tolyl-3-oxopyrazolidine, 1-p-methoxyphenol-3- oxopyrazolidine, 1 phenol-4-ethyl-3-oxopyrazolidine, 1- phenol 4-isopropyl-3-oxopyrazolidine, 1-phenol-4,4-dimethyl 3-oxopyrazolidine, l-phenol-5-methyl-3-oxopyrazolidine, 1 phenol 5,S-dimethyl-3-oxopyrazolidine, 1- phenol-4,5-dimethyl-3-oxopyrazolidine, and 1,5-diphenol- 3-oxopyrazolidine.
  • said polymer image is a colored image obtained by dyeing said polymer image which contains a member selected from the group consisting of an acidic and a basic group with a dye having an acidity or basicity opposite to that of said polymer.
  • A represents an oxygen atom or an imino group
  • B represents a phenyl group or a substituted phenyl group
  • R R and R each represents a hydrogen atom or an alkyl group having 1-6 carbon atoms
  • R represents a hydrogen atom, an alkyl group having 1-6 carbon atoms, an aryl group, or a carboxyl group.
  • said reducing agent is a member selected from the group consisting of resorcinol, a m-amino-phenol, a naphthol, a pyrazoline- S-one, and a phenol.
  • said reducing agent is a member selected from the group consisting of resorcinol, N,N-dimethylmethaminophenol, 3,4-dimethyl- 5-pyrazolone, and o-xylenol.
  • said pyrazolidine compound is a member selected from the group consisting of 1 phenol-3-oxopyrazolidine, 1-phenol-4-methyl-3- oxopyrazolidine, 1-phenol-3-oxopyrazolidine-S-carboxylic acid, 1 p-tolyl-3-oxopyrazolidine, 1-p-methoxyphenol-3- oxopyrazolidine, 1 phenol-4-ethyl-3-oxopyrazolidine, 1- phenol-4-ethyl-3-oxopyrazolidine, 1-phenol-4-isopropyl-3- oxopyrazolidine, 1-phenol-4,4-dimethyl-3-oxopyrazolidine, 1 phenol S-methyl-3-oxopyrazolidine, 1-phenol-5,5-dimethyl 3-oxopyrazolidine, 1-phenol-4,S-dimethyl-B-oxopyrazolidine, and 1,5-diphenol-3-oxopyra
  • said vinyl or vinylidene compound is a member selected from the group consisting of acrylamide, acrylonitrile, N-hydroxymethylacrylamide, methacrylic acid, acrylic acid, calcium acrylate, sodium acrylate, methacrylamide, methylmethacrylate, methylacrylate, ethylacrylate, vinylpyrrolidone, vinylmethylether, vinylbutylether, vinylisopropylether, vinyl isobutyl ether, vinyl butyrate, 2 vinyl-pyridine, 4-vinylpyridine, 2-methyl-N-vinylimidazole, potassium vinyl benzene sulfonate, vinyl carbazole, N,N'-methylene bis acrylamide, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, divinyl ether, and divinyl benzene.
  • said polymer image is a colored image obtained by dyeing said polymer image having a member selected from the group consisting of an acidic or a basic group with a dye having an acidity or basicity opposite to that of said polymer.

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
US825347A 1968-05-16 1969-05-16 Process for the formation of photographic images Expired - Lifetime US3707379A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3957515A (en) * 1974-03-15 1976-05-18 La Cellophane Photographic process for producing colored polymerized images
US6387136B1 (en) 1998-07-20 2002-05-14 L'oreal S.A. Compositions for dyeing keratin fibers, containing 3-aminopyrazoline derivatives as coupler, dyeing process and dyeing kit

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS55149939A (en) * 1979-04-05 1980-11-21 Asahi Chem Ind Co Ltd Image forming method and photosensitive material used for it

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3957515A (en) * 1974-03-15 1976-05-18 La Cellophane Photographic process for producing colored polymerized images
US6387136B1 (en) 1998-07-20 2002-05-14 L'oreal S.A. Compositions for dyeing keratin fibers, containing 3-aminopyrazoline derivatives as coupler, dyeing process and dyeing kit

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FR2008665A1 (enrdf_load_html_response) 1970-01-23
BE732981A (enrdf_load_html_response) 1969-10-16
DE1924721A1 (de) 1969-12-04
GB1269715A (en) 1972-04-06

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