US3258338A - Photographic material containing softening agent - Google Patents

Photographic material containing softening agent Download PDF

Info

Publication number
US3258338A
US3258338A US162272A US16227261A US3258338A US 3258338 A US3258338 A US 3258338A US 162272 A US162272 A US 162272A US 16227261 A US16227261 A US 16227261A US 3258338 A US3258338 A US 3258338A
Authority
US
United States
Prior art keywords
compound
gelatin
softening agent
mol
layer
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
Application number
US162272A
Inventor
Claeys Daniel Alois
Willems Jozef Frans
Vrancken Marcel Nicolas
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.)
Individual
Original Assignee
Individual
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from DEG32594A external-priority patent/DE1146362B/en
Application filed by Individual filed Critical Individual
Application granted granted Critical
Publication of US3258338A publication Critical patent/US3258338A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/40—Esters thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • 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
    • G03C1/31—Plasticisers
    • 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
    • G03C1/38—Dispersants; Agents facilitating spreading
    • 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
    • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/14—Dimensionally stable material

Definitions

  • This invention relates to a process for improving the physical properties of a photographic material and more particularly to an improved process for softening gelatin containing layers of such a photographic material.
  • gelatin photographic materials it is important to incorporate softening agents to the gelatin for rendering the gelatin layers made therefrom better resistant to treatments at a low relative humidity. Indeed, gelatin layers or gelatin containing layers without softening agents are very brittle at low degree of relative humidity.
  • gelatin polyalcohols such as glycerol, lactic acid, substituted phenols monoglycerides of fatty acids or amides such as formanilide as a softening agent.
  • water-soluble long-chained aliphatic amines containing an amide function As compounds improving the elasticity and the flexibility of gelatino silver halide emulsion layers, water-soluble long-chained aliphatic amines containing an amide function, metal soaps of sulfonated caster oil which are insoluble in the photographic processing baths, poly(methXy alcohols) and aqueous dispersions of poly(ethyl acrylate) are also added.
  • glycerol or other polyalcohols are strongly hygroscopic and thus injure the photographic and physical properties of the layers at rather high relative humidity.
  • Softening agents for articles made of proteinaceous material are not numerous since the compatibility of the softening agents with the proteinaceous material is mostly insufiicient.
  • softening agents for gelatin used for photographic purposes, there has moreover to be paid attention to their possible influence on the photographic properties of the materials to be manufactured. In some cases the transparency of the material should not be injured by the addition of softening agents.
  • the phosphonic acid compounds and phosphoric acid compounds used according to the invention correspond to the following general formula:
  • R and R represents an alkyl radical or an R (O-alkylene) radical, preferably an radial,
  • R represents a hydroxyl group, an alkyl radical, an
  • alkoxy radical or an R -(Oalkylene) -O-- radical preferably an R -(O-CH CH ),,O radical, wherein R represents an alkyl radical, an alkaryl radical or an acyl radical,
  • n an integer of from 1 to 50.
  • the phosphonic and phosphoric acid compounds used according to this invention can easily be prepared from the corresponding acid chlorides or acid anhydrides by reaction with higher as well as with lower alcohols, with monoalkylene glycol alkylethers or with polyoxyalkylene glycol monoalkyl ethers.
  • COMPOUND l.TRIETHYL ORTHOPHOSPHORIC ACID ESTER This compound is marketed as Triethyl Phosphate by Albright & Wilson, Ltd., London.
  • COMPOUND 3.-TRIETHY'L PHOSPHONIC ACID ESTER This compound is marketed as Diethyl ethyl phosphonate by Virginia-Carolina Chemical Corporation, Richmond, Va., U.S.A.
  • COMPOUND 7.-TRI(DIETHYLENE GLYCOL MONOETHYL ETHER) PHOSPHATE In a three-necked flask of 3 liter, fitted with a stirrer, a thermometer, a condenser, a dropping funnel and the necessary calcium chloride tubes, the following mixture is stirred and cooled till 0 C.:
  • the formed mixture consisting of two layers is first heated for 30 min., then cooled and finally extracted with ether for 8 hours.
  • the obtained ether-extract is dried over anhydrous sodium sudfate and after drying the ether is distilled.
  • the residue is then kept for 2 hours on a water bath in the reduced pressure formed by a water-jet pump in order to eliminate the remained traces of pyridine, if still present.
  • a mixture consisting of g. of tridecycloxy pentadecaethylene glycol, 4 g. of pyridine, 25 g. of phosphorus oxychloride and 50 cm. of benzene is refluxed for 1 hr. After cooling, the formed pyridine hydrochloride is filtered oif and hydrochloric gas is led through the benzene solution. After filtration, the benzene solution is stirred and boiled with 10 0111. of water and then evaporated to dryness.
  • COMPOUND 12 The softening agent with the following composition:
  • COMPOUND 15 The softening agent with the following composition A mixture consisting of 20 g. of the condensation product of 15 mol of ethylene oxide, 1 mol of nonyl phenyl, 0.8 g. of dry phosphorous pentoxide and cm. of anhydrous ether is refluxed for 2 hr. Thereupon the ether is distilled.
  • COMPOUND 16 The softening agent with the following composition COMPOUND 17
  • the softening agents can be used in various compositions of matter. They are especially suited for being incorporated in gelatin containing layers which form part of a photographic material.
  • the phosphonic and phosphoric acid compounds according to the invention can favorably be applied in a photographic silver halide emulsion layer or in another gelatin containing layer of a light sensitive photographic material such as an antihalation layer or other backing layer or supercoat on the emulsion layer as well as in gelatin containing layers of an image-receiving material for the manufacture of' images according to the silver complex diffusion transfer process described in US. patent specification 2,352,014.
  • These softening agents can also favorably be used in the gelatin layer of the socalled blank film described in French patent specification 1,265,552.
  • These layers may comprise compounds such as colour couplers, chemical or optical sensitizers, anti-fogging agents, optical brightening agents, wetting agents, development accelerators and matting agents, and can be cast upon paper, glass plates or films e.g. of cellulose esters, polyesters, polystyrene, etc.
  • the softening agents according to this invention have also a good antistatic effect. This eifect is strongly pronounced when the softening agent is incorporated into a layer which is in the outer side of the photographic material such as a backing layer.
  • softening agents according to the present invention are equally well suited for being applied in lightsensitive silver halide emulsion layers.
  • Softening agents with a molecular weight of more than 1500 and having more than 20 oxyalkylene groups in their structure when applied in the light-sensitive silver halide emulsion layer in an amount as small as possible in order to obtain a practically usable softening effect give already rise to formation of fog.
  • Such softening agents can be used in another layer than the silver halide emulsion layer of a photographic material.
  • the amount of softening agent which can be used de pends on the desired improvement of the flexibility of the layers wherein they are incorporated.
  • these compounds are used in an amount of 10% to 30% based on the weight of dry proteinaceous material.
  • the phosphonic and phosphoric acid compounds ac cording to this invention are preferably added before coating the gelatin solution.
  • some of these compounds with no more than alkylene oxide groups are preferably emulsified in the gelatin solution by means of emulsifying agents.
  • the most suitable emulsifying agents are the anionactive wetting agents such as sodium salts of alkylsulfonic acids e.g. sodium tetradecylsulfate and the sodium salt of the condensation product of oleic acid and methyltaurine of the formula
  • anionactive wetting agents such as sodium salts of alkylsulfonic acids e.g. sodium tetradecylsulfate and the sodium salt of the condensation product of oleic acid and methyltaurine of the formula
  • Example 1 The equal parts of a aqueous solution of gelatin at pH 7 to 8, of the compounds identified in the following table, based on the weight of the dry gelatin, are added. After thoroughly mixing the gelatin solutions are applied onto glass-plates which are treated previously in such a way that after drying, the gelatin layers can easily be stripped off.
  • the gelatin layers with a thickness of about 150 m are stripped off and cut into strips with a width of 15 mm. Thereupon the number of folds until breaking are determined with a M.I.T. fold tester at relative humidity and 20 C.
  • Example 2 160 cm? of a 10% alcoholic solution of compound 8 are added to 1 kg. of a light-sensitive silver halide emulsion comprising g. of gelatin. This emulsion is cast onto a cellulose triacetate support and dried.
  • the number of folds until breaking of the emulsion strips determined at 30% relative humidity and 20 C. with a M.I.T. fold tester amounts to 20.
  • a similar emulsion strip without softening breaks at the fourth fold.
  • Example 3 LAYER A To 1 liter of a 8% aqueous solution of gelatin containing an anti-halation dyestuif, cm. of a 10% alcoholic solution of the softening agent described as compound 8 in Example 1 are added. The solution is applied onto a cellulose triacetate support and dried.
  • LAYER B To 1 liter of a 8% aqueous solution of gelatin containing manganese dioxide, 150 cm. of a 10% alcoholic solution of the softening agent described as compound 8 in Example 1 are added. The solution is applied onto a cellulose triacetate support and dried.
  • Photographic material comprising a support and at least one gelatin layer containing a compound of the formula:
  • each of R and R represents an alkyl radical or a R (O-alkylene) radical
  • R represents a hydroxyl group, an alkyl radical, an
  • alkoxy radical or a R (O-alkylene),,O-- radical wherein R represents an alkyl radical, an alkaryl radical or an acyl radical, and n represents an integer of from 1 to 50,
  • said compound being present in a quantity of at least 3% by weight of the gelatin.
  • Photographic material according to claim 1 comprising at least one gelatino silver halide emulsion layer and at least one other gelatin layer free of silver halide emulsion, and wherein each of said gelatino emulsion layer and said other gelatin layer contain a compound corresponding to the formula of claim 1 in an amount equal to at least 3% by weight of the gelatin therein.
  • the photographic material of claim 1 wherein said layer contains a compound of the formula 0-(0 HzO H2O)4 lauryl O PO-(CH2C HzO-)4 lauryl 7.
  • R and R each represents an R (O-alkylene) radical or an R CO(O-alkylene) radical R represents a hydroxyl group
  • R represents a hydrocarbon radical
  • n represents a positive number from 1 to 50.
  • Sheet metal according to claim 8 wherein said compound is present in an amount equal to at least 3% by weight of the gelatin in said layer.
  • Sheet material according to claim 10 wherein the 14.
  • the sheet material of Claim 8 wherein said layer contains a mixture of of a compound of the formula 15.
  • the sheet material of claim 8, wherein said layer contains a compound of the formula References Cited by the Examiner UNITED STATES PATENTS 2,887,381 5/1959 Levy 9694 2,940,854 6/1960 Gray 9694 2,950,980 8/1960 Hirsch 106125 2,958,605 11/1960 Leineretal 106125 3,058,941 10/1962 Birum 106 OTHER REFERENCES Buttrey, D. N., Plasticizers, London, Cleaver-Hume Press Ltd., 1957, pp. 35, 36.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Spectroscopy & Molecular Physics (AREA)

Description

United States Patent ()fi ice 3,258,338 Patented June 28, 1966 3,258,338 PHOTOGRAPIHC MATERIAL CONTAINING SOFTENING AGENT Daniel Alo'is Claeys, Guido Gezellelaan 104, Mortsel- Antwerp, Belgium; Jozef Frans Willems, Sterrenlaan 52, Wilrijk-Antwerp, Belgium; and Marcel Nicolas Vrancken, Ringlaan 31, Berchem-Antwerp, Belgium No Drawing. Filed Dec. 26, 1961, Ser. No. 162,272 Claims priority, application Belgium, Dec. 29, 1960,
40,328, Patent 598,619; June '26, 1961, 40,757; Germany, June 27, 1961, G 32,594
16 Claims. (Cl. 96-67) This invention relates to a process for improving the physical properties of a photographic material and more particularly to an improved process for softening gelatin containing layers of such a photographic material.
When using gelatin photographic materials it is important to incorporate softening agents to the gelatin for rendering the gelatin layers made therefrom better resistant to treatments at a low relative humidity. Indeed, gelatin layers or gelatin containing layers without softening agents are very brittle at low degree of relative humidity.
It is known to add to gelatin polyalcohols such as glycerol, lactic acid, substituted phenols monoglycerides of fatty acids or amides such as formanilide as a softening agent.
As compounds improving the elasticity and the flexibility of gelatino silver halide emulsion layers, water-soluble long-chained aliphatic amines containing an amide function, metal soaps of sulfonated caster oil which are insoluble in the photographic processing baths, poly(methXy alcohols) and aqueous dispersions of poly(ethyl acrylate) are also added.
As softening agents for gelatin it is further known to use compounds with a substituted amide group as described in French patent specification 1,114,721.
Some of these products such as glycerol or other polyalcohols are strongly hygroscopic and thus injure the photographic and physical properties of the layers at rather high relative humidity.
Softening agents for articles made of proteinaceous material are not numerous since the compatibility of the softening agents with the proteinaceous material is mostly insufiicient.
In choosing softening agents for gelatin used for photographic purposes, there has moreover to be paid attention to their possible influence on the photographic properties of the materials to be manufactured. In some cases the transparency of the material should not be injured by the addition of softening agents.
The use of phosphoric acid esters such as tributyl phosphate, tricresyl phosphate and triphenyl phosphate as softening agents for articles containing cellulose esters is already known since a long time (Kirk-Othmer, Encyclopedia of Chemical Technology, p. 766).
It has now been found that some organic compounds of phosphonic acid and phosphoric acid are excellent softening agents for articles of proteinaceous materials such as gelatin or casein, and that these softening agents soften layers containing proteinaceous materials if they are added thereto in an amount of at least 3% by weight of the dry proteinaceous material.
The phosphonic acid compounds and phosphoric acid compounds used according to the invention correspond to the following general formula:
wherein Each of R and R represents an alkyl radical or an R (O-alkylene) radical, preferably an radial,
R represents a hydroxyl group, an alkyl radical, an
alkoxy radical or an R -(Oalkylene) -O-- radical, preferably an R -(O-CH CH ),,O radical, wherein R represents an alkyl radical, an alkaryl radical or an acyl radical,
And n represents an integer of from 1 to 50.
Mixtures of softening agents according to the above general formula can also be used.
The phosphonic and phosphoric acid compounds used according to this invention can easily be prepared from the corresponding acid chlorides or acid anhydrides by reaction with higher as well as with lower alcohols, with monoalkylene glycol alkylethers or with polyoxyalkylene glycol monoalkyl ethers.
The following compounds and some of their preparations illustrate the present invention. Many of these compounds are commercially available.
COMPOUND l.TRIETHYL ORTHOPHOSPHORIC ACID ESTER This compound is marketed as Triethyl Phosphate by Albright & Wilson, Ltd., London.
COMPOUND 2.TRI-N-BUTYL ORTHOPHOS- PHORIC ACID ESTER This compound is marketed as Tri-n-butyl Phosphate by Albright & Wilson, Ltd, London.
COMPOUND 3.-TRIETHY'L PHOSPHONIC ACID ESTER This compound is marketed as Diethyl ethyl phosphonate by Virginia-Carolina Chemical Corporation, Richmond, Va., U.S.A.
COMPOUND 4.TRI(2-METIIOXYETHYLENE) PHOSPHATE In a three-necked flask of 5 liter fitted with a stirrer, a thermometer, a condenser, a dropping funnel and the necessary calcium chloride tubes, the following mixture is stirred and cooled till 0 C.:
228 g. (3 mol) of ethyleneglycol monomethyl ether 237 g. (3 mol) of pyridine 1000 c. of anhydrous benzene While the temperature is kept between 0 and 5 C., 154 g. (1 mol) of phosphorus oxychloride are dropwise added in two hours, whereby a precipitate of pyridine hydrochloride is formed. The mixture is still stirred for one hour. Thereupon 500 cm. of water are added and the formed benzene layer is separated. The benzene is distilled on a water-bath under a fractionating column with the air of the reduced pressure of a water-jet pump in order to collect the main fraction of the residue having a boiling range of 202-218 C. at 15 mm. Hg of pressure. After renewed distillation by means of an oil vacuum pump, the desired fraction is obtained which distills between 158 and 160 C. at about 1 mm. Hg of pressure.
3 COMPOUND 5 .--TRI (Z-ETHOXYETHYLENE) PHOSPHATE In a three-necked flask of 5 liter fitted with a stirrer, a thermometer, a condenser, a dropping funnel and the necessary calcium chloride tubes, the following mixture is stirred and cooled till C.:
270 g. (3 mol) of ethylene glycol monoethylether 237 g. (3 mol) of pyridine 1000 c. of anhydrous benzene While the temperature is kept between 0 and C., 154 g. (1 mol) of phosphoroxychloride are dropwise added in two hours, whereby a precipitate of pyridine hydrochloride is formed. The mixture is still stirred for one hour. Thereupon 500 cm. of water are added and the formed benzene layer is separated. The benzene is distilled on a water-bath under a fractionating column with the aid of the reduced pressure of a water-jet pump. The residue is first distilled at about 1 mm. Hg of pressure without fractionation and thereupon fractionated at the same pressure in order to collect the fraction with boiling range of 150158 C.
Yield: 78 g.
COMPOUND 6.TRI(DIETHYLENE GLYCOL MONOMETHYL ETHER) PHOSPHATE In a three-necked flask of 3 liter fitted with a stirrer, a thermometer, a condenser, a dropping funnel and the necessary calcium chloride tubes the following mixture is stirred and cooled till 0 C.:
252 g. (2.1 mol) of diethylene glycol monomethyl ether 237 g. (3 mol) of pyridine 1000 cm. of anhydrous benzene While the temperature is kept between 0 and 5 C., 154 g. (1 mol) of phosphorus oxychloride are dropwise added in two hours, whereby a precipitate of pyridine hydrochloride is formed. The mixture is still stirred for one hour and thereupon 500 cm. of water are added. The benzene layer is separated and the benzene is distilled on a water-bath under a fractionating column with the aid of the reduced pressure of a water-jet pump. The residue is distilled at about 1 mm. Hg of pressure in order to collect the main fraction with boiling range of 150-158 C. Yield: 78 g.
COMPOUND 7.-TRI(DIETHYLENE GLYCOL MONOETHYL ETHER) PHOSPHATE In a three-necked flask of 3 liter, fitted with a stirrer, a thermometer, a condenser, a dropping funnel and the necessary calcium chloride tubes, the following mixture is stirred and cooled till 0 C.:
402 g. (3 mol) of diethylene glycol monoethyl ether 237 g. (3 mol) of pyridine 1000 cm. of anhydrous benzene While the temperature is kept between 0 and 5 C., 154 g. (1 mol) of phosphorus oxychloride are dropwise added in two hours. The mixture is still stirred for 1 hr. The formed pyridine hydrochloride is sucked off and washed with anhydrous benzene. The benzene filtrate is evaporated with the aid of a water-jet vacuum pump whereby a pale yellow oil is left. Then the carbitol residue is removed by extraction with hexane, whereupon 80 cm. of 5 N sodium hydroxide are added. The formed mixture consisting of two layers is first heated for 30 min., then cooled and finally extracted with ether for 8 hours. The obtained ether-extract is dried over anhydrous sodium sudfate and after drying the ether is distilled. The residue is then kept for 2 hours on a water bath in the reduced pressure formed by a water-jet pump in order to eliminate the remained traces of pyridine, if still present.
Yield: 150 g.
4 COMPOUND 8 The softening agent with the following composition:
O(O HrOH2O)aCiaH21 The softening agent with the following composition /O(CH2 2O)15 i3 27 O=PO(CH:CH2O)i5Ci3H27 is prepared as follows:
A mixture consisting of g. of tridecycloxy pentadecaethylene glycol, 4 g. of pyridine, 25 g. of phosphorus oxychloride and 50 cm. of benzene is refluxed for 1 hr. After cooling, the formed pyridine hydrochloride is filtered oif and hydrochloric gas is led through the benzene solution. After filtration, the benzene solution is stirred and boiled with 10 0111. of water and then evaporated to dryness.
COMPOUND 10 The softening agent with the following composition O(CH2CH3O)5O O-C17Has is prepared as follows:
A mixture consisting of 20 g. of the condensation product of 5 mol of ethylene oxide and 1 mol of stearic acid, 50 cm. of anhydrous ether and 0.95 g. of dry phosphorus pentoxide is refluxed for 2 hr. Thereupon the ether is distilled.
COMPOUND 11 The softening agent with the following composition is prepared as follows:
A mixture consisting of 20 g. of the condensation product of 10 mol of ethylene oxide and 1 mol of stearic acid, 50 cm. of anhydroux ether and 0.66 g. of dry phosphorus pentoxide is refluxed for 2 hr. Thereupon the ether is distilled.
COMPOUND 12 The softening agent with the following composition:
O(C Hz-C H2O) 15C O-O17H35 is prepared as follows:
A mixture consisting of 20 g. of the condensation product of 15 mol of ethylene oxide and 1 mol of stearic acid, 50 cm. of anhydrous ether and 0.51 g. of anhydrous phosphorus pentoxide is refluxed for 2 hr. Thereupon the ether is distilled.
COMPOUND 13 The softening agent with the following composition 2CH2O)5oCOO17 s5 is prepared as follows:
A mixture consisting of 20 g. of the condensation product of 50 mol of ethylene oxide and 1 mol of stearic acid, 50 cm. of anhydrous ether and 0.20 g. of dry phosphorous pentoxide is refluxed for 2 hr. Thereupon the ether is distilled.
, COMPOUND 14 The softening agent with the following composition is prepared as follows:
A mixture consisting of 16 g. of the condensation product of 6 mol of ethylene oxide and 1 mol of nonyl phenol, 50 cm. of anhydrous ether and 1.2 g. of dry phosphorous pentoxide is refluxed for 2 hr. Thereupon the ether is distilled.
COMPOUND 15 The softening agent with the following composition A mixture consisting of 20 g. of the condensation product of 15 mol of ethylene oxide, 1 mol of nonyl phenyl, 0.8 g. of dry phosphorous pentoxide and cm. of anhydrous ether is refluxed for 2 hr. Thereupon the ether is distilled.
COMPOUND 16 The softening agent with the following composition COMPOUND 17 The softening agent with the general formula O(CH2CH2O)4 lauryl O='PO(CH2-C HzO) lauryl is marketed under the trade-name Hostaphat KL 240 by Farbwerke Hoechst A.G., Frankfurt am Main Hochst, Germany.
COMPOUND 18 The softening agent with the general formula O(C Hg CH2O-)s oleyl 0=P0 (0 Hz-CHz-O oleyl OH is marketed under the trade-name Hostaphat KO 280 by Farbwerke Hoechst A.G., Frankfurt am Main Hochst, Germany.
The softening agents, according to the present invention can be used in various compositions of matter. They are especially suited for being incorporated in gelatin containing layers which form part of a photographic material.
The phosphonic and phosphoric acid compounds according to the invention can favorably be applied in a photographic silver halide emulsion layer or in another gelatin containing layer of a light sensitive photographic material such as an antihalation layer or other backing layer or supercoat on the emulsion layer as well as in gelatin containing layers of an image-receiving material for the manufacture of' images according to the silver complex diffusion transfer process described in US. patent specification 2,352,014. These softening agents can also favorably be used in the gelatin layer of the socalled blank film described in French patent specification 1,265,552. These layers may comprise compounds such as colour couplers, chemical or optical sensitizers, anti-fogging agents, optical brightening agents, wetting agents, development accelerators and matting agents, and can be cast upon paper, glass plates or films e.g. of cellulose esters, polyesters, polystyrene, etc.
The softening agents according to this invention have also a good antistatic effect. This eifect is strongly pronounced when the softening agent is incorporated into a layer which is in the outer side of the photographic material such as a backing layer.
Not all softening agents according to the present invention are equally well suited for being applied in lightsensitive silver halide emulsion layers. Softening agents with a molecular weight of more than 1500 and having more than 20 oxyalkylene groups in their structure, when applied in the light-sensitive silver halide emulsion layer in an amount as small as possible in order to obtain a practically usable softening effect give already rise to formation of fog. Such softening agents, however, can be used in another layer than the silver halide emulsion layer of a photographic material.
The amount of softening agent which can be used de pends on the desired improvement of the flexibility of the layers wherein they are incorporated. Preferably these compounds are used in an amount of 10% to 30% based on the weight of dry proteinaceous material.
The phosphonic and phosphoric acid compounds ac cording to this invention are preferably added before coating the gelatin solution. In order to obtain a good dispersion some of these compounds with no more than alkylene oxide groups, are preferably emulsified in the gelatin solution by means of emulsifying agents.
The most suitable emulsifying agents are the anionactive wetting agents such as sodium salts of alkylsulfonic acids e.g. sodium tetradecylsulfate and the sodium salt of the condensation product of oleic acid and methyltaurine of the formula In order to compare the increased flexibility of gelatin containing layers containing softening agents according to this invention with the flexibility of usually treated gelatin layers folding tests were carried out with a M.I.T. f-old tester. By means of this apparatus the number of folds until breaking can be determined.
The following examples illustrate the present invention.
Example 1 The equal parts of a aqueous solution of gelatin at pH 7 to 8, of the compounds identified in the following table, based on the weight of the dry gelatin, are added. After thoroughly mixing the gelatin solutions are applied onto glass-plates which are treated previously in such a way that after drying, the gelatin layers can easily be stripped off.
After solidifying and drying at room-temperature, the gelatin layers with a thickness of about 150 m are stripped off and cut into strips with a width of 15 mm. Thereupon the number of folds until breaking are determined with a M.I.T. fold tester at relative humidity and 20 C.
The following results are obtained:
Number of folds Softening agent: until breaking None 6 Glycerol 18 Compound 1 64 Compound 2 Compound 3 12 Compound 4 32 Compound 5 77 Compound 6 38 Compound 7 Compound 8 286 Compound 9 35 Compound 10 117 Compound 11 22 Compound 12 15 Compound 13 26 Compound 14 46 Compound 15 22 Compound 16 36 Compound 17 119 Compound 18 85 8 The compounds 1, 3, 4, 5, 6 and 7 were added to the gelatin solution by means of the emulsifying agent Tergitol 4 (trade-name for a 25% aqueous solution of sodium tetradecyl sulfate marketed by Union Carbide and Carbon, New York, N.Y., U.S.A.).
Example 2 160 cm? of a 10% alcoholic solution of compound 8 are added to 1 kg. of a light-sensitive silver halide emulsion comprising g. of gelatin. This emulsion is cast onto a cellulose triacetate support and dried.
The number of folds until breaking of the emulsion strips determined at 30% relative humidity and 20 C. with a M.I.T. fold tester amounts to 20. A similar emulsion strip without softening breaks at the fourth fold.
Example 3 LAYER A To 1 liter of a 8% aqueous solution of gelatin containing an anti-halation dyestuif, cm. of a 10% alcoholic solution of the softening agent described as compound 8 in Example 1 are added. The solution is applied onto a cellulose triacetate support and dried.
LAYER B To 1 liter of a 8% aqueous solution of gelatin containing manganese dioxide, 150 cm. of a 10% alcoholic solution of the softening agent described as compound 8 in Example 1 are added. The solution is applied onto a cellulose triacetate support and dried.
The flexibility of both anti-halation layers is tested with a M.I.T. fold tester at 20 C. and at 30% and 36% relative humidity. Two layers C and D, prepared in the same way as the layers A and B but containing no softening agent, are also tested. The following results are obtained:
1. Photographic material comprising a support and at least one gelatin layer containing a compound of the formula:
each of R and R (equal or different) represents an alkyl radical or a R (O-alkylene) radical,
R represents a hydroxyl group, an alkyl radical, an
alkoxy radical, or a R (O-alkylene),,O-- radical wherein R represents an alkyl radical, an alkaryl radical or an acyl radical, and n represents an integer of from 1 to 50,
said compound being present in a quantity of at least 3% by weight of the gelatin.
2 Photographic material according to claim 1 wherein said one gelatin layer is a gelatino silver halide emulsion layer, said compound being present in an amount equal to at least 3% by weight of the gelatin in said layer.
3. Photographic material according to claim 1 comprising at least one gelatino silver halide emulsion layer and at least one other gelatin layer free of silver halide emulsion, and wherein each of said gelatino emulsion layer and said other gelatin layer contain a compound corresponding to the formula of claim 1 in an amount equal to at least 3% by weight of the gelatin therein.
4. The photographic material of claim 1 wherein said layer contains a mixture of 80% of a compound of the formula 5. The photographic material of claim 1 wherein said layer contains a mixture of 90% of a compound of the formula O(CHzCHa-O)C OC17H35 O=PO-(CH2CH2O)5C o C11H35 O-(OHZCH2O)5COC17H35 and of a compound of the formula O-(C H2CH2O)5C OC11H35 O=PO(CH2CHzO)5COG17H 6. The photographic material of claim 1 wherein said layer contains a compound of the formula 0-(0 HzO H2O)4 lauryl O=PO-(CH2C HzO-)4 lauryl 7. The photographic material of claim 1 wherein said layer contains a compound of the formula O-(C Hz-C Hz0)s oleyl 0=1 o-(o H -C HzO)s oleyl 8. Sheet material comprising a support and at least one gelatin layer containing a compound of the formula:
0R1 O=]!-O R:
wherein R and R each represents an R (O-alkylene) radical or an R CO(O-alkylene) radical R represents a hydroxyl group, an
radical or an R --CO'(O-alkylene) O radical in which formula R represents a hydrocarbon radical, and n represents a positive number from 1 to 50.
9. Sheet metal according to claim 8, wherein said compound is present in an amount equal to at least 3% by weight of the gelatin in said layer.
10. Sheet material according to claim 8, wherein n represents a positive number of 3 to 8.
11. Sheet material according to claim 10, wherein the 14. The sheet material of Claim 8, wherein said layer contains a mixture of of a compound of the formula 15. The sheet material of claim 8, wherein said layer contains a compound of the formula 16. The sheet material of claim 8, wherein said layer contains a compound of the formula References Cited by the Examiner UNITED STATES PATENTS 2,887,381 5/1959 Levy 9694 2,940,854 6/1960 Gray 9694 2,950,980 8/1960 Hirsch 106125 2,958,605 11/1960 Leineretal 106125 3,058,941 10/1962 Birum 106 OTHER REFERENCES Buttrey, D. N., Plasticizers, London, Cleaver-Hume Press Ltd., 1957, pp. 35, 36.
NORMAN G. TORCHIN, Primary Examiner.
ALEXANDER D. RICCI, Examiner.
C. E. DAVIS, Assistant Examiner.
UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,258,338 June 28, 1966 Daniel Alois Claeys et al.
It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.
In the grant, line 4, after "Belgium," insert assignors to Gevaert Photo-Producten N.V. of Mortsel Belgium, a company of Belgium lines 13 and 14, for "Daniel Alois Claeys, Jozef Frans Willems, and Marcel Nicolas Vrancken, their heirs" read Gevaert Photo-Producten N.V. its successors in the heading to the printed specification, lines 4 to 7, for "Daniel Alois Claeys, Guido Gezellelaan 104, Mortsel-Antwerp, Belgium; Jozef Frans Willems, Sterrenlaan 52, Wilrijk-Antwerp, Belgium; and Marcel Nicolas Vrancken, Ringlaan 31, Berchem-Antwerp, Belgium" read Daniel Alois Claeys Mortsel-Antwerp, Belgium; Jozef Frans Willems, Wilrijk- Antwerp, Belgium; and Marcel Nicolas Vrancken, Berchem- Antwerp Belgium, assignors to Gevaert Photo-Producten N.V. Mortsel, Belgium, a company of Belgium Signed and sealed this 25th day of March 1969.
(SEAL) Attest:
EDWARD M.FLETCHER,JR. EDWARD J. BRENNER Attesting Officer Commissioner of Patents

Claims (1)

1. PHOTOGRAPHIC MATERIAL COMPRISING A SUPPORT AND AT LEAST ONE GELATIN LAYER CONTAINING A COMPOUND OF THE FORMULA:
US162272A 1960-12-29 1961-12-26 Photographic material containing softening agent Expired - Lifetime US3258338A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
BE40382 1960-12-29
BE40757 1961-06-26
DEG32594A DE1146362B (en) 1960-12-29 1961-06-27 Process for improving the physical properties of a photographic material

Publications (1)

Publication Number Publication Date
US3258338A true US3258338A (en) 1966-06-28

Family

ID=27158410

Family Applications (1)

Application Number Title Priority Date Filing Date
US162272A Expired - Lifetime US3258338A (en) 1960-12-29 1961-12-26 Photographic material containing softening agent

Country Status (4)

Country Link
US (1) US3258338A (en)
BE (2) BE605378A (en)
GB (1) GB1009187A (en)
NL (1) NL272967A (en)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3332777A (en) * 1963-01-04 1967-07-25 Ciba Ltd Silver halide emulsion preparation using phosphoric acid esters as flocculants
US3364044A (en) * 1962-08-20 1968-01-16 Agfa Ag Gelatine compositions containing pentaerythritol esters of phosphoric acids
US3380826A (en) * 1964-07-23 1968-04-30 Sylvania Electric Prod Fabrication of image display screens
US3443951A (en) * 1964-07-02 1969-05-13 Agfa Gevaert Nv Photographic light-sensitive materials containing phosphoric acid ester of aliphatic polyols
US3547650A (en) * 1967-11-13 1970-12-15 Du Pont Silver halide emulsion comprising a gelatin - polyvinyl compound dispersion
US3607289A (en) * 1965-03-17 1971-09-21 Agfa Gevaert Ag Gelatin emulsions having improved properties
US3655387A (en) * 1970-09-15 1972-04-11 Eastman Kodak Co Antistatic photographic compositions
US4211836A (en) * 1978-01-23 1980-07-08 Fuji Photo Film Co., Ltd. Method for dispersing oil-soluble photographic additives
FR2494861A1 (en) * 1980-11-26 1982-05-28 Wolfen Filmfab Veb PROCESS FOR THE INCORPORATION OF HYDROPHOBIC PHOTOGRAPHIC ADDITIVES IN ACQUIRED MEDIA
US4353979A (en) * 1979-07-25 1982-10-12 Konishiroku Photo Industry Co., Ltd. Light-sensitive silver halide photographic materials

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0019896B1 (en) * 1979-06-01 1985-10-02 American Hoechst Corporation Colour testing foil

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2887381A (en) * 1957-07-29 1959-05-19 Levy Marilyn Sensitized photographic substances
US2940854A (en) * 1956-08-16 1960-06-14 Eastman Kodak Co Gelatin silver halide emulsion plasticized with dicarboxylic acid esters
US2950980A (en) * 1958-09-10 1960-08-30 Hirsch Arthur Adhesive compositions
US2958605A (en) * 1958-07-22 1960-11-01 Union Carbide Corp Adhesive compositions
US3058941A (en) * 1959-12-14 1962-10-16 Monsanto Chemicals Compositions comprising an organic polymer and an organo phosphorus compound

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2940854A (en) * 1956-08-16 1960-06-14 Eastman Kodak Co Gelatin silver halide emulsion plasticized with dicarboxylic acid esters
US2887381A (en) * 1957-07-29 1959-05-19 Levy Marilyn Sensitized photographic substances
US2958605A (en) * 1958-07-22 1960-11-01 Union Carbide Corp Adhesive compositions
US2950980A (en) * 1958-09-10 1960-08-30 Hirsch Arthur Adhesive compositions
US3058941A (en) * 1959-12-14 1962-10-16 Monsanto Chemicals Compositions comprising an organic polymer and an organo phosphorus compound

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3364044A (en) * 1962-08-20 1968-01-16 Agfa Ag Gelatine compositions containing pentaerythritol esters of phosphoric acids
US3332777A (en) * 1963-01-04 1967-07-25 Ciba Ltd Silver halide emulsion preparation using phosphoric acid esters as flocculants
US3443951A (en) * 1964-07-02 1969-05-13 Agfa Gevaert Nv Photographic light-sensitive materials containing phosphoric acid ester of aliphatic polyols
US3380826A (en) * 1964-07-23 1968-04-30 Sylvania Electric Prod Fabrication of image display screens
US3607289A (en) * 1965-03-17 1971-09-21 Agfa Gevaert Ag Gelatin emulsions having improved properties
US3547650A (en) * 1967-11-13 1970-12-15 Du Pont Silver halide emulsion comprising a gelatin - polyvinyl compound dispersion
US3655387A (en) * 1970-09-15 1972-04-11 Eastman Kodak Co Antistatic photographic compositions
US4211836A (en) * 1978-01-23 1980-07-08 Fuji Photo Film Co., Ltd. Method for dispersing oil-soluble photographic additives
US4353979A (en) * 1979-07-25 1982-10-12 Konishiroku Photo Industry Co., Ltd. Light-sensitive silver halide photographic materials
FR2494861A1 (en) * 1980-11-26 1982-05-28 Wolfen Filmfab Veb PROCESS FOR THE INCORPORATION OF HYDROPHOBIC PHOTOGRAPHIC ADDITIVES IN ACQUIRED MEDIA

Also Published As

Publication number Publication date
NL272967A (en)
BE598619A (en)
BE605378A (en)
GB1009187A (en) 1965-11-10

Similar Documents

Publication Publication Date Title
US3258338A (en) Photographic material containing softening agent
EP0265196B1 (en) The stabilization of dye images produced in photographic materials
EP0337784B1 (en) The stabilization of dye images produced in photographic materials
US3443946A (en) Photographic material having a roughened protective layer
JPH01536A (en) photographic coating composition
US5616768A (en) Process for purifying phosphoric esters
US4097560A (en) Novel phosphorus compounds and flame retardant compositions containing same
JPH02142A (en) Water-soluble surface active compound
US3658573A (en) Support provided with antistatic layer
US4794072A (en) Phosphate ester stabilizers
US2807636A (en) Polyesters of phosphoryl-substituted alcohols and polybasic phosphorus acids
US2617820A (en) Alkyl benzyl tetrachlorophthalates
US3502474A (en) Process for producing photographic light-sensitive elements
US3554755A (en) Photographic emulsions containing chemical adjuvants dispersed in crystalloidal solvents
US3255013A (en) Increasing the sensitivity of photographic emulsions
EP0479260A2 (en) Cellulose ester film containing phosphoric ester plasticizer and aromatic carboxylic ester
US2304890A (en) Triarylmethane compound
US3300337A (en) Anti-static coated textile fiber
US3756828A (en) Es photographic light sensitive material having good antistatic properti
US3428456A (en) Antistatic photographic materials
US3364044A (en) Gelatine compositions containing pentaerythritol esters of phosphoric acids
US3413123A (en) Gelatine compositions containing alkylene oxide hydrophobic plasticizers
US3342903A (en) Pentaerythritol phosphoric acid esters
US3135609A (en) 1-hydroxy-2-naphthamide couplers for color photography
US3264108A (en) Antistatic photographic film