US3189459A - Photographic composition containing epoxy hardening agents - Google Patents

Photographic composition containing epoxy hardening agents Download PDF

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Publication number
US3189459A
US3189459A US244898A US24489862A US3189459A US 3189459 A US3189459 A US 3189459A US 244898 A US244898 A US 244898A US 24489862 A US24489862 A US 24489862A US 3189459 A US3189459 A US 3189459A
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United States
Prior art keywords
parts
bis
gelatin
epoxypropyl
solution
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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US244898A
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English (en)
Inventor
Donald M Burness
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Eastman Kodak Co
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Eastman Kodak Co
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Filing date
Publication date
Priority to BE630602D priority Critical patent/BE630602A/xx
Priority to BE620602D priority patent/BE620602A/xx
Priority to US810571A priority patent/US3091537A/en
Priority to FR904878A priority patent/FR1329435A/fr
Priority to GB46993/62A priority patent/GB1086331A/en
Application filed by Eastman Kodak Co filed Critical Eastman Kodak Co
Priority to US244898A priority patent/US3189459A/en
Application granted granted Critical
Publication of US3189459A publication Critical patent/US3189459A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/10—Polycondensates containing more than one epoxy group per molecule of polyamines with epihalohydrins or precursors thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/28—Di-epoxy compounds containing acyclic nitrogen atoms
    • 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
    • G03C1/306—Hardeners containing an oxirane ring

Definitions

  • compositions thereof are provided.
  • One object of my invention is to provide for the hardening of gelatin or other polymeric materials used in photographic layers by incorporating quaternary ammonium compounds, containing at least two epoxide groups therein, in compositions of the polymeric materials.
  • Another object of my invention is to provide gelatin or other polymeric products having carboxyl and/or amino groups therein with hardening agents which are. non-volatile, stable in aqueous solution and non-fat soluble. Other objects of my invention will appear herein.
  • quaternary ammonium compounds containing at least two epoxide groups therein exhibit satisfactory hardening properties when used in gelatin compositions employed either as carriers for silver halidephotographic emulsions or for applying layers in the manufacture of photographic products. I have found in addition that these compounds exert a hardening effect upon carboxyl-bearing polymers useful for the purposes speci-
  • the quaternary ammonium salts containing at least two epoxide groups therein are used as hardeners in an amount at least-%% based on the weight of the gelatin or other polymeric material. In practice, not more than percent is needed, based on gelatin weight.
  • proportions, however, of the hardeners in accordance with my invention are not critical, in that proportions less than have been found to exhibit a hardening effect on gelatin or carboxylbearing polymers and on the other hand proportions thereof greater than 10 percent will result in a hardening effect when incorporated in compositions of gelatin or other carboxyl containing polymers.
  • The-anion of the quaternary ammonium salts may be BEST AVAILABLE COPY ICC that of any convenient'acid, although because of casein 7 their preparation, the perchlorate and sulfonate salts have been preferred. However, the chloride, sulfate, phosphate or the like may be employed for hardening purposes to good effect.
  • the quaternary ammonium salts useful for hardening may be entirely aliphatic or they may contain cyclo aliphatic groups or aromatic groups therein. -In some cases, cyclic compounds containing nitrogen in the ring may be used to supply the nitrogen for-the quaternary ammonium structure ofthe hardener.
  • the amine may consist of any of the lower aliphatic or aromatic primary amines and the alkylating agent may be selected from the alkyl sulfonates, sulfates, halides, or the like.
  • the alkylating agent may be selected from the alkyl sulfonates, sulfates, halides, or the like.
  • certain heterocyclic amines such as piperidine or morpholine may BEST AVAILABLE'C'OPY housed. .ln Equation 3 the bisull'onatc might contain unsaturation; hetero atoms or ringr; or the corresponding dihalide might be used.
  • Other di-stcondary amines can be employed in place of the piperazine in Equation 4.
  • the polymeric compounds which may be hardened by quaternary ammonium compounds containing bisepoxide groups in accordance with the invention are those containing amino and/or carboxyl'groups. Many of these polymers havebeen used for supplying coatings in the manufacture of photographic products or as carriers for silver halides in' photographic emulsions, such as gelatin, celluloseether phthalate and synthetic resins. Gelatin and carboxyl containing polymers are readily hardenable by incorporating quaternary ammonium compounds therein in accordance with our invention.
  • 2,725,293 as being useful as carriers for silver halide are hardenable by means of quaternary ammonium compounds in accordance with my invention.
  • polymers containing carboxyl groups hardenable by quaternary ammonium compounds as described herein are ammonium salts of poly(butyl-acrylate coacrylic acid), sodium salts of phthalated polyvinyl alcohohammonium salts of phthalated gelatin, ammonium salts of phthalated polyvinyl alcohol, ammonium salts of copolymers of acrylic acid (30-40 mol percent) and one or more of the following esters; butyl methacrylate,
  • hardeners as described herein are incorporated in compositions of these polymers and the compositions are coated out onto a surface and the coating is dried, such as by warm dry air, hardening of the polymeric material takes place in a short time as evidenced by improved resistance to the efiect of hot water and by an appreciable increase in the melting point ofthe coating as compared with the same polymeric material in which no hardener has been incorporated.
  • the polymeric layer is hardened by the quaternary ammonium compound upon standing or aging such as for two or three days at normal temperature. With curing at an elevated temperature hardening results in a shorter time.
  • the quaternary ammonium salts prepared in accordance with the above examples were incorporated in aqueous gelatin compositions which were coated out onto support in the form of a layer thereon.
  • the melting properties of these layers were compared with those of The designations 212-1 and 212-2 indicate that it was necessary to hold the temperature at boiling for one or two minutes, respectively, before any melting of the gelatin layer was observed.
  • EXAMPLE IV 222 parts of epichlorohydrin at 25 C; was added dropwise to 121 parts of a 40 percent solution of methylamine in water. Cooling was necessary to hold the temperature at 20-30 during the addition and for three hours thereafter. 208 parts of a solution of 50 percent sodium hydroxide was then added at a temperature of less than 25 C. and the mass was stirred for 1% hours. The top layer which formed was separated and was combined with ether extracts of the bottom aqueous layer and the mass was dried over potassium hydroxide pellets for several days. The mass was filtered and distilled at reduced pressure (20 mm.) at 104-107 C.
  • EXAMPLE V A solution of 102 parts of piperazine in 100 parts of The mixture was 'cooled, filtered, and the mixture was washed with ligroin. The product was recrystallized from 1200 parts of ethyl acetate giving 106 parts of colorless 'bischlorohydrin (M.P. 1015-103); The filtrate was cooled to 60 C. producing 16 parts of isomeric bischlorohydrin, having a melting point of 82-84 C.
  • the product obtained was a quaternary ammonium salt designated as 1,4-bis(2,3- cpoxypropyl)-1,4-dimethyl piperazinium di-p-toluene sulfonate.
  • EXAMPLE VT N,N-bis(2,3-epoxypropyl)ethylamine was obtained by the procedure described in the first part of Example I except that ethylamine was employed instead of propylamine. This material was reacted with methyl paratoluene sultonate in the manner similar to that described in Example I. There was obtained a 48 percent solution of quaternary salt designated bis(2,3-epoxypropyl)ethyl-methyl ammonium paratoluene sulfonate.
  • Hardcner on wt. of gelatin in emulsion
  • Age at 607 2.0% bls(2.3-epoxy ropyl)mcthyl propyl ammonium p-to ucnesulfonate.
  • ammounlum p-tolucnesullonate ammounlum p-tolucnesullonate
  • EXAMPLE VII 5 parts of a 48 percent solution of the quaternary ammonium salt prepared in Example VI was mixed with a solution of 2 parts of sodium tetraphenyl boride in 15 parts of water. The percipitate which formed gradually crystallized when the mass was cooled by an ice bath.
  • the product was purified by recrystallizing from acetone.
  • gelatin and was found to measurably decrease the percent swelling of coatings thereof by aqueous liquids.
  • Dev. Fir Wash .4 13 Stripped 80 74 92 78 none 98 118 93 none 106 130 108 none Mushiness is an internal physical measurement test and concerns the placement of a pointer directly over the emulsion side of a film sample.
  • the pointer touches the emulsion surface, thesample being present in either developer, fixer or water, with no weight attached to it. Subscquently increasing gram weights are added to the top of the pointer so that increasing pressures are'cxerted on the emulsion.
  • the number of grams on the pointer at the time the emulsion first ruptures indicates its resistance to pressure. High mushiness values are advantageous; .low mushiness values are disadvantageous.
  • the following three examples relate to the preparation of compounds. containing a plurality of epoxy groups which are useful as hardeners for gelatin and for carboxyl containing polymers.
  • the coatings contained 1040 mg. of gelatin per square foot, each emulsion sample being coated on a cellulose acetate film support at a silver coverage of 459 mg. per square foot.
  • a sample of each film coating was exposed on an Eastman lB Sensitometer, processed for 5 minutes in Kodak DK-SO developer, fixed, washed and dried. It was found that the emulsion coatings showed a substantial increase in resistance to swelling by water as compared with emulsion coatings not containing hardener.
  • ammonium salts are most conveniently added to gelatin solutions in the form of aqueous solutions.
  • some other solvent may be employed in admixture with water. If the solution of quaternary is to be stored for a long period of time it is ordinarily preferable to dissolve in some other solvent than water.
  • coating compositions having a pH within the range of 5-9 the effective aging time is substantially uniform.
  • the polyepoxide salts are useful not only as hardeners for gelatin but also for hardening carboxyl-containing polymers.
  • One polymer of this type is the water soluble salt of a carboxy cster-lactone of an interpolymer of an unsaturated alpha-beta-dicarboxylic acid and a vinyl ester of a carboxylic acid which is ordinarily used in the form of its water soluble salt.
  • a solution was prepared in water of 5% of this carboxyl-containing polymer, 0.15% bis(2,3-epoxypropyl) dimethylammoniurn p-tosylate and 0.05% p-tert.-octylphen0xy diethoxyethyl sodium sulfonate.
  • the pH of the solution was adjusted to 7.
  • This solution was coated onto a' gelatin subbed cellulose triacetate film base and was dried by blowing hot air over the surface ofthe coating.
  • Another coating was prepared in identical manner except that the epoxy compound was omitted. Strips of both coatings were aged for seven days at 77 F. and 50% and thewet adhesion of these coatings on the film base was determined by immersing the coatings in dilute alkali and distilled water. The coating which contained the epoxy compound was insoluble in both solutions. The coating without the epoxy compound dissolved off of the support instantaneously.
  • the vertical swell of the two coatings was measured in a mildly alkaline developer after different periods of incubation at 77 F, and RE.
  • the epoxy containing coating after one day's incubation had a vertical swell of 750%; that after seven days incubation and that after days incubation both had a vertical swell of 300%.
  • the coating without the epoxy compound therein dissolvcd in the developer.
  • compositions were prepared using aqueous solutions of the water soluble salt of a carboxy esterlactone of an interpolymer of an unsaturated alpha-betadicarboxylic acid and a vinyl ester of a carboxylic acid and each of the following cross-linking agents were added to separate portions respectively:
  • a photographic element comprising a layer which contains cellulose ether phthalate having a phthalyl content of at least 20% by weight and as a hardener therefor, a quaternary ammonium salt containing at least two oxirane rings separated from the quaternary nitrogen by a single carbon atom.
  • composition of matter comprising a water-soluble salt of a carboxy ester-lactonc of an interpolymer of an unsaturated alpha-beta dicarboxylic acid and a vinyl ester of a carboxylic acid and a hardening amount of p-xylylene bis[N,N-bis-(2,3-epoxypropyl)-N-methyl-ammonium perchlorate].
  • composition of matter comprising a water-soluble salt of a carboxy ester-lactone of'an interpolymer of an unsaturated alpha-beta dicarboxylic acid and a vinyl ester of a carboxylic acid and a hardening amount of bis(2,3- epoxypropyl) dimethyl ammonium p-toluene sulfonate.
  • a composition useful forapplying layers in the preparation of photographic products which comprise a 5%' solution in water of a water-soluble salt of a carboxy esterlactone of an interpolymer of an unsaturated alphabeta-dicarboxylic acid and a vinyl ester of a carboxylic acid which solution contains 0.15% of bis(2,3-epoxypropyl) dimcthylammonium 'p-tosylate and 0.05% p-tert.-octylphcnoxy diethoxyethyl sodium sulfonate.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Epoxy Compounds (AREA)
  • Epoxy Resins (AREA)
US244898A 1959-05-04 1962-12-17 Photographic composition containing epoxy hardening agents Expired - Lifetime US3189459A (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
BE630602D BE630602A (en, 2012) 1962-07-24
BE620602D BE620602A (en, 2012) 1962-07-24
US810571A US3091537A (en) 1959-05-04 1959-05-04 Hardening of photographic layers
FR904878A FR1329435A (fr) 1962-07-24 1962-07-24 Procédé de tannage des compositions photographiques et nouveaux produits obtenus
GB46993/62A GB1086331A (en) 1962-07-24 1962-12-12 Method of hardening photographic layers
US244898A US3189459A (en) 1962-07-24 1962-12-17 Photographic composition containing epoxy hardening agents

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR904878A FR1329435A (fr) 1962-07-24 1962-07-24 Procédé de tannage des compositions photographiques et nouveaux produits obtenus
GB46993/62A GB1086331A (en) 1962-07-24 1962-12-12 Method of hardening photographic layers
US244898A US3189459A (en) 1962-07-24 1962-12-17 Photographic composition containing epoxy hardening agents

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US3189459A true US3189459A (en) 1965-06-15

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BE (2) BE630602A (en, 2012)
FR (1) FR1329435A (en, 2012)
GB (1) GB1086331A (en, 2012)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3380998A (en) * 1963-06-03 1968-04-30 Takeda Chemical Industries Ltd Cellulose derivatives and their application for coating agents
US3656956A (en) * 1968-01-30 1972-04-18 Fuji Photo Film Co Ltd Silver halide photographic light-sensitive material
US4017473A (en) * 1974-05-24 1977-04-12 Agfa-Gevaert N.V. Hardening of proteinaceous materials
US4025349A (en) * 1974-03-18 1977-05-24 Eastman Kodak Company Silver halide photographic elements spectrally sensitized with an acetylenic analog of cyanine or merocyanine dyes
US4239851A (en) * 1978-02-02 1980-12-16 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive material

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2725293A (en) * 1952-04-01 1955-11-29 Eastman Kodak Co Photographic emulsion compositions and their preparation
US2861056A (en) * 1953-11-12 1958-11-18 Eastman Kodak Co Resinous carboxy ester-lactones and process for preparing them
US3091537A (en) * 1959-05-04 1963-05-28 Eastman Kodak Co Hardening of photographic layers

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2725293A (en) * 1952-04-01 1955-11-29 Eastman Kodak Co Photographic emulsion compositions and their preparation
US2861056A (en) * 1953-11-12 1958-11-18 Eastman Kodak Co Resinous carboxy ester-lactones and process for preparing them
US3091537A (en) * 1959-05-04 1963-05-28 Eastman Kodak Co Hardening of photographic layers

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3380998A (en) * 1963-06-03 1968-04-30 Takeda Chemical Industries Ltd Cellulose derivatives and their application for coating agents
US3656956A (en) * 1968-01-30 1972-04-18 Fuji Photo Film Co Ltd Silver halide photographic light-sensitive material
US4025349A (en) * 1974-03-18 1977-05-24 Eastman Kodak Company Silver halide photographic elements spectrally sensitized with an acetylenic analog of cyanine or merocyanine dyes
US4017473A (en) * 1974-05-24 1977-04-12 Agfa-Gevaert N.V. Hardening of proteinaceous materials
US4239851A (en) * 1978-02-02 1980-12-16 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive material

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BE620602A (en, 2012)
GB1086331A (en) 1967-10-11
FR1329435A (fr) 1963-06-07
BE630602A (en, 2012)

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JPS60659B2 (ja) ゼラチンの硬化方法