US3888681A - Process for the rapid hardening of gelatin - Google Patents

Process for the rapid hardening of gelatin Download PDF

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Publication number
US3888681A
US3888681A US281095A US28109572A US3888681A US 3888681 A US3888681 A US 3888681A US 281095 A US281095 A US 281095A US 28109572 A US28109572 A US 28109572A US 3888681 A US3888681 A US 3888681A
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United States
Prior art keywords
acid
diazine
gelatin
hardener
chloro
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Expired - Lifetime
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US281095A
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English (en)
Inventor
Ikutaro Horie
Kameji Nagao
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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
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/30—Hardeners
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/74—Applying photosensitive compositions to the base; Drying processes therefor

Definitions

  • ABSTRACT A process for the rapid hardening of gelatin comprising coating a support with an aqueous gelatin solution containing as a hardener at least one of a halogenated diazine compound, a halogenated triazine compound, a compound having an active vinyl radical, a mucohalogen acid or a derivative thereof and a substituted or an unsubstituted 2,3-dihydroxy-1, 4-dioxane, drying at a constant rate for a period of time and irradiating with a high frequency microwaves is disclosed.
  • gelatin is used as a material for, e.g., a binder for the silver halide emulsion, a protective colloid layer, an intermediate layer, an under coat layer for the film base, an antihalation layer, a backing layer, etc.
  • the light sensitive material having some of these layers containing gelatin is treated with treating liquids of var ious compositions under various conditions after exposure. If the layers containing gelatin of the photographic material are not treated with a hardener in the treatments as described above, they have a poor water resistance and are swollen excessively by the treatments and tend to be damaged. Occasionally gelatin is dissolved off of the support with a treatment at a high temperature. These situations damage greatly the performance of the light sensitive material.
  • Various kinds of gelatin hardeners have been used previously to eliminate these disadvantages of gelatin.
  • inorganic compounds such as chromium alum as well as organic compounds such as aldehyde compounds, active vinyl compounds and ethyleneimino compounds are known. These hardeners may be added to the emulsion or the treating liquid depending upon the purpose.
  • hardeners require a very long reaction time to harden the gelatin sufficiently, so that a considerably long time has been required to obtain the desired physical properties (for example, water resistance and mechanical strength, such as abrasion resistance etc. of the photographic gelatin layer) and the desired photographic properties (for example, for density, maximum density etc.) in the light sensitive material.
  • desired physical properties for example, water resistance and mechanical strength, such as abrasion resistance etc. of the photographic gelatin layer
  • desired photographic properties for example, for density, maximum density etc.
  • This invention relates to a process for the rapid hardening of gelatin comprising coating a support, such as a synthetic resin film, a glass or a paper, with an aqueous gelatin solution containing at least one of a halogen substituted diazine and a halogen substituted traizine compound, a compound having an active vinyl radical, a mucohalogen acid or a derivative thereof, and a substituted and an unsubstituted 2, 3-dihydroxy-1,4-dioxane, and after drying at a constant rate for a periodof time, irradiating with high frequency microwaves.
  • a support such as a synthetic resin film, a glass or a paper
  • halogenated diazine and triazine compounds as a hardener which can be used in this invention are those described in U.S. Pat. Nos. 2,983,611, 3,325,287 and 3,549,377, and British Pat. Nos.
  • 1,072,008 and 1,193,290 for example, 4-chlor0- 2 2,6-bis(methylsulfonyl)-1,3-diazine, 4-chloro-2- ethylsulfonyl-6-methyl-1 ,3-diazine,2,4-dibromo-6- methylsulfonyl- 1 ,3-diazine,2,4,5-tribromo-6- methylsulfonyl- 1 ,3-diazine,4,5-dichloro-6-methy1-2- phenylsulfonyl-l ,3-diazine, 2,3-dichloroquinoxaline-6- carboxylic acid chloride, 2,3-dichloroquin0xaline-6- chloro-7-sulfonic acid chloride, N,N-bis(hydroxyethyl- )aminodichlorotriazine, the sodium salt of 2,4- dichloro-6-oxy-stria
  • suitable examples are those described in U.S. Pat. Nos. 3490911 and 3539644, and British Pat. No. 994,869, for example, methylene bisacrylamide, 1,2-bis(2- vinylsulfonylmethoxy)ethane, or bis(2-vinylsulfonylethyl)ether and the like.
  • Suitable mucohalogen acids and their derivatives are those' described in U.S. Pat. Nos. 2,080,019 and- 3,579,374 and Belgian Pat. No. 725,964, for example, mucochloric acid, mucobromic acid, 3-bromo-2- phenoxymalealdehydic acid, 3-chloro-2- phenoxymalealdehydic acid, 2-(p-carboxyphenoxy)-3- chloromalealdehydic acid, 2-(p-methoxyphenoxy)-3- chloromalealdehydic acid, 2-(p-tert-pentylphenoxy-3- chloromalealdehydic acid, 2-(p-octylphenoxy)-3- chloromalealdehydic acid, 2-(m-pentadecyl)-3- chloromalealdehydic acid, or 3-chloro-2-phenylthiomalealdehydic acid and the like.
  • substituted and unsubstituted 2,3-dihydroxy- 1,4-dioxanes suitable examples are those described in U.S. Pat. No. 2,870,013, British Pat. No. 1,270,578 (corresponding to U.S. patent application Ser. No. 201,999 filed Nov. 24, 1971 which is a continuation application of U.S. patent application Ser. No. 850,673 filed Aug. 15, 1969), German Offenlegungsschrift No. 2,104,816 (corresponding to U.S. patent application Ser..No. 112,014 filed Feb.
  • 2, 1971 for example, 2,3-dihydroxy-1,4-dioxane, 5-chloromethyl-2,3-dihydroxy-l ,4-dioxane, 5-phenoxymethyl-2,3-dihydroxy- 1,4-dioxane,2-methyl-2,3-dihydroxy-1, 4-dioxane, 2,5 6-trimethyl-2,3-dihydroxy-1,4-dioxane, and the like.
  • the aqueous gelatin solutions include gelatin solutions, acetylated gelatin solutions and succinated gelatin solutions and also includes use as, for example, coating solutions for silver halide emulsion layers, protective colloid layers, intermediate layers, under coat layers for film bases, antihalation layers and backing layers.
  • These layers of the photographic sensitive material contain gelatin, and it is also applicable to gelatin solutions for encapsulating microcapsules and the like.
  • the photographic gelatin layers can contain various additives such as coating aids, anti-foggants, chemical sensitizers, spectral sensitizers, plasticizers, such as glycerine, dicarboxylic acid esters described in U.S. Pat. No. 2,940,854, lower alkyl esters of ethylene bisglycolic acid described in U.S. Pat. No. 2,904,434, couplers, swelling controlling agents such as those de- 3 scribed in U.S. Defensive Publication No. T873,003 (April 7, 1970) and antistatic agents.
  • coating aids such as coating aids, anti-foggants, chemical sensitizers, spectral sensitizers, plasticizers, such as glycerine, dicarboxylic acid esters described in U.S. Pat. No. 2,940,854, lower alkyl esters of ethylene bisglycolic acid described in U.S. Pat. No. 2,904,434, couplers, swelling controlling agents such as those de
  • drying at a constant rate for a period of time will be illustrated as follows: If a support is coated with an aqueous solution of gelatin and dried at a constant temperature and humidity, the water content during the drying process is reduced initially in proportion to the time and the rate of reduction in the water content is then gradually lowered (that is, the water content is reduced initially at a constant rate and then at a falling rate); the former drying stage is described as drying at a constant rate for a period of time.
  • the irradiation with a high frequency electric field can be carried out after the drying at the constant rate and therefore, the application of a high frequency electric field after the completion of the drying provides good results without losing the effects of this invention.
  • a suitable frequency which can be from are those bands designated [MS bands having frequencies of 13.56MHZ 27.12MHz, 40.68MHz, 915MHz, 24.50MHz, 58.50MHz, 10600MHz, and 18000MHz. Use of frequencies of 2450MHz and 915MHz as approved by various governmental agencies for industrial use are suitably used to obtain the effects of this invention.
  • the irradiation time with the high frequency microwaves which may vary depending on the intensity of the high frequency electric field generally is preferably from 1 sec. to 20 min.
  • the hardening reaction of gelatin is promoted to reduce the reaction time so that the physical and photographic properties of the photo graphic light sensitive material having gelatincontaining layers are constant resulting in an improved performance of the material with great advantages.
  • EXAMPLE 1 A gelatin-silver iodide emulsion (containing 0.3 mol of silver halide per kg of emulsion), in which the gelatin content was adjusted to and which contained silver bromide particles which had been previously goldand sulfur-sensitized (containing 5 mol% of silver iodide), was prepared. Subsequently, the following Compounds (1) to (4) in the amounts indicated per g of the emulsion were added.
  • EXAMPLE 2 mg of 2-methoxy-4,6-dichloro-s-triazine per g of dried gelatin were added to a gelatin-silver chlorobromide emulsion having silver chlorobromide particles containing 40 mol% of silver chloride (containing 50g of gelatin and 0.38 mol of silver halide per Kg of emulsion), a photographic support was coated with the mixture so that the dried thickness of coating would be 5p. and the procedures (a) to (g) as described in Example 1 were carried out to yield Samples (a) to (f). The melting point of the emulsion film of each sample was determined in a 2% aqueous solution of sodium carbonate and the results as shown in Table 2 were obtained.
  • EXAMPLE 5 Instead of 2,4-dimethoxy-6-chloro-s-triazine used in Example 3, 10mg of hexahydro-l ,3,5-triacryl-s-triazine and 2mg of the sodium salt of 2-oxy-4,6-dichloro-striazine per g of dried gelatin were added and the same procedure as described in Example 3 was carried out.
  • EXAMPLE 7 Instead of the sodium salt of 2-oxy-4, 6-difluoro-striazine in Example 1, 5mg of 2,3-dihydroxy-l ,4- dioxane per g of dried gelatin were added and the same procedure as described in Example 6 was carried out. The melting point of the emulsion film of each sample in a 2% aqueous solution of sodium'carbonate was determined and the result obtained are as shown in Table 7.
  • EXAMPLE 8 b lrradiating Sample (a) with a high frequency for 30 sec.
  • a process for the rapid hardening of gelatin comprising coating a support with an aqueous gelatin solution containing as a hardener at least one of a halogenated diazine compound, a halogenated triazine compound, a compound having an active vinyl radical, a mucohalogen acid or a derivative thereof and a substituted or an unsubstituted 2,3-dihydroxy-1,4-dioxane, drying the coating at a constant rate for a period of time without irradiating and then after completion of the constant rate drying period, irradiating with high frequency microwaves.
  • said hardener is 4-chloro-2, 6-bis(methylsulfonyl)-1 ,3-diazine, 4- chloro-2-ethylsulfonyl-6-methyll ,3-diazine, 4,6- bis(methylsulfonyl)-1,3-diazine, 2,4-dibromo-6- methylsulfonyl- 1 ,3-diazine, 2,4,5-tribromo-6-methylsulfonyl-l 3-diazine, 4,5,6-tris(methylsulfonyl)-l ,3- diazine, 4,5-dichloro-6-methyl-2-phenylsulfonyl-1 ,3- diazine, 2,3-dichloroquinoxaline-6-carboxylic acid chloride, 2,3-dichloroquinoxaline-6-chloro-7-sulfonic acid chloride, N,
  • said hardener is acrylamide, vinyl sulfone, diacryloylamine, dipotassium l, 4-di (a-bromoacryloylamino)benzene-2,5- disulfonate, naphthalene-4,6-disulfonate, or N-p-( B- chloroethylamino)-sulfobenzene acrylamide.
  • said hardener is mucochloric acid, mucobromic acid, 3-bromo-2- phenoxymalealdehydic acid, 3-chloro-2- phcnoxymalealdehydic acid, 2-(p-carboxyphenoxy)-3- chloromalealdehydic acid, 2-(p-methoxyphenoxy)-3- chloromalealdehydic acid, 2-(p-tert-pentylphenoxy-3- chloromalealdehydic acid, 2-(p-octylphenoxy)-3- chloromalealdehydic acid, 2-(m-pentadecyl)-3- chloromalealdehydic acid, or 3-chloro-2-phenylthiomalealdehydic acid.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
US281095A 1971-08-23 1972-08-16 Process for the rapid hardening of gelatin Expired - Lifetime US3888681A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4149322A (en) * 1976-08-27 1979-04-17 Fuji Photo Film Co., Ltd. Drying concentration of photographic emulsion coating by microwave irradiation
DE3106409A1 (de) * 1980-02-22 1982-01-07 Fuji Photo Film Co., Ltd., Minami-Ashigara, Kanagawa Vorlaeufer fuer lichtempfindliche lithographische druckplatten
US4680257A (en) * 1983-03-07 1987-07-14 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive material
US20130161936A1 (en) * 2010-09-17 2013-06-27 Fujifilm Manufacturing Europe B.V. Photographic Paper

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5751202B2 (en)) * 1973-11-20 1982-10-30
JPS5832576B2 (ja) * 1976-10-28 1983-07-14 協和醗酵工業株式会社 ゼラチンの改質法
JPH0799429B2 (ja) * 1984-03-26 1995-10-25 コニカ株式会社 ハロゲン化銀写真感光材料

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2662302A (en) * 1950-02-07 1953-12-15 Cunningham Method and apparatus for drying film by dielectric heating
US2725305A (en) * 1952-01-02 1955-11-29 Eastman Kodak Co Hardening gelatin emulsions and gelatin solutions
US3288775A (en) * 1961-04-07 1966-11-29 Ciba Ltd Method of hardening gelatin by reacting with conjugated heterocyclic compounds containing halogen atoms and water-solubilizing acid groups
US3426439A (en) * 1967-02-16 1969-02-11 Houston Fearless Corp Microwave drying system
US3480440A (en) * 1965-06-11 1969-11-25 Agfa Gevaert Ag Hardening of photographic gelatin-containing layers
US3507661A (en) * 1966-08-03 1970-04-21 Minnesota Mining & Mfg Gelatin containing dispersions having gelatin reactive polymers therein and coatings prepared therefrom
US3689274A (en) * 1968-02-16 1972-09-05 Agfa Gevaert Ag Process of hardening photographic gelatin layers with a sulfonyl ester or a sulfonamide
US3729318A (en) * 1970-07-25 1973-04-24 Agfa Gevaert Ag Process for cross-linking silver halide gelatino emulsion layer containing non-diffusible compound having epoxide and isocyanate groups

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2662302A (en) * 1950-02-07 1953-12-15 Cunningham Method and apparatus for drying film by dielectric heating
US2725305A (en) * 1952-01-02 1955-11-29 Eastman Kodak Co Hardening gelatin emulsions and gelatin solutions
US3288775A (en) * 1961-04-07 1966-11-29 Ciba Ltd Method of hardening gelatin by reacting with conjugated heterocyclic compounds containing halogen atoms and water-solubilizing acid groups
US3480440A (en) * 1965-06-11 1969-11-25 Agfa Gevaert Ag Hardening of photographic gelatin-containing layers
US3507661A (en) * 1966-08-03 1970-04-21 Minnesota Mining & Mfg Gelatin containing dispersions having gelatin reactive polymers therein and coatings prepared therefrom
US3426439A (en) * 1967-02-16 1969-02-11 Houston Fearless Corp Microwave drying system
US3689274A (en) * 1968-02-16 1972-09-05 Agfa Gevaert Ag Process of hardening photographic gelatin layers with a sulfonyl ester or a sulfonamide
US3729318A (en) * 1970-07-25 1973-04-24 Agfa Gevaert Ag Process for cross-linking silver halide gelatino emulsion layer containing non-diffusible compound having epoxide and isocyanate groups

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4149322A (en) * 1976-08-27 1979-04-17 Fuji Photo Film Co., Ltd. Drying concentration of photographic emulsion coating by microwave irradiation
DE3106409A1 (de) * 1980-02-22 1982-01-07 Fuji Photo Film Co., Ltd., Minami-Ashigara, Kanagawa Vorlaeufer fuer lichtempfindliche lithographische druckplatten
US4680257A (en) * 1983-03-07 1987-07-14 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive material
US20130161936A1 (en) * 2010-09-17 2013-06-27 Fujifilm Manufacturing Europe B.V. Photographic Paper

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FR2150407A1 (en)) 1973-04-06
JPS5248148B2 (en)) 1977-12-07
DE2240982A1 (de) 1973-03-01
GB1364763A (en) 1974-08-29
JPS4830754A (en)) 1973-04-23
FR2150407B1 (en)) 1976-08-13

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