US3769022A - Photosensitive silver halide emulsions comprising coating aids - Google Patents
Photosensitive silver halide emulsions comprising coating aids Download PDFInfo
- Publication number
- US3769022A US3769022A US00092495A US3769022DA US3769022A US 3769022 A US3769022 A US 3769022A US 00092495 A US00092495 A US 00092495A US 3769022D A US3769022D A US 3769022DA US 3769022 A US3769022 A US 3769022A
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- US
- United States
- Prior art keywords
- photographic element
- element according
- silver halide
- salts
- coating
- 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
Links
- -1 silver halide Chemical class 0.000 title claims abstract description 51
- 239000000839 emulsion Substances 0.000 title claims abstract description 34
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 18
- 239000004332 silver Substances 0.000 title claims abstract description 18
- 238000000576 coating method Methods 0.000 title description 48
- 239000011248 coating agent Substances 0.000 title description 47
- 239000000084 colloidal system Substances 0.000 claims abstract description 28
- 125000006353 oxyethylene group Chemical group 0.000 claims abstract description 17
- 150000003839 salts Chemical group 0.000 claims abstract description 17
- 239000004094 surface-active agent Substances 0.000 claims abstract description 17
- 239000002253 acid Substances 0.000 claims abstract description 14
- 229920000151 polyglycol Polymers 0.000 claims abstract description 12
- 239000010695 polyglycol Substances 0.000 claims abstract description 12
- 239000011230 binding agent Substances 0.000 claims abstract description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 5
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 25
- 108010010803 Gelatin Proteins 0.000 claims description 19
- 229920000159 gelatin Polymers 0.000 claims description 19
- 239000008273 gelatin Substances 0.000 claims description 19
- 235000019322 gelatine Nutrition 0.000 claims description 19
- 235000011852 gelatine desserts Nutrition 0.000 claims description 19
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 150000007513 acids Chemical class 0.000 claims description 7
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 7
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 6
- 229920000570 polyether Polymers 0.000 claims description 6
- 235000011149 sulphuric acid Nutrition 0.000 claims description 5
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 238000004383 yellowing Methods 0.000 abstract description 6
- 239000010410 layer Substances 0.000 description 39
- 239000008199 coating composition Substances 0.000 description 19
- 229910052708 sodium Inorganic materials 0.000 description 12
- 239000011734 sodium Substances 0.000 description 12
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- SBIRNPJIWVWCEG-UHFFFAOYSA-N 12-methyltridecyl hydrogen sulfate Chemical compound CC(C)CCCCCCCCCCCOS(O)(=O)=O SBIRNPJIWVWCEG-UHFFFAOYSA-N 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000001397 quillaja saponaria molina bark Substances 0.000 description 5
- 229930182490 saponin Natural products 0.000 description 5
- 150000007949 saponins Chemical class 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 229940125782 compound 2 Drugs 0.000 description 4
- 239000011241 protective layer Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 229910021607 Silver chloride Inorganic materials 0.000 description 3
- 150000005840 aryl radicals Chemical class 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229940125898 compound 5 Drugs 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 3
- 241001479434 Agfa Species 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 229920001477 hydrophilic polymer Polymers 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- SYXUBXTYGFJFEH-UHFFFAOYSA-N oat triterpenoid saponin Chemical compound CNC1=CC=CC=C1C(=O)OC1C(C=O)(C)CC2C3(C(O3)CC3C4(CCC5C(C)(CO)C(OC6C(C(O)C(OC7C(C(O)C(O)C(CO)O7)O)CO6)OC6C(C(O)C(O)C(CO)O6)O)CCC53C)C)C4(C)CC(O)C2(C)C1 SYXUBXTYGFJFEH-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910021653 sulphate ion Inorganic materials 0.000 description 2
- ZWHOTPNCEFWATE-CQSZACIVSA-N (3R)-3-[4-(aminomethyl)-6-(trifluoromethyl)pyridin-2-yl]oxy-N-phenylpyrrolidine-1-carboxamide Chemical compound NCC1=CC(=NC(=C1)C(F)(F)F)O[C@H]1CN(CC1)C(=O)NC1=CC=CC=C1 ZWHOTPNCEFWATE-CQSZACIVSA-N 0.000 description 1
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 1
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 description 1
- 208000030507 AIDS Diseases 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 101150065749 Churc1 gene Proteins 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 102100038239 Protein Churchill Human genes 0.000 description 1
- 229910021612 Silver iodide Inorganic materials 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003831 antifriction material Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 1
- 229910001864 baryta Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 229920003090 carboxymethyl hydroxyethyl cellulose Polymers 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 229940105329 carboxymethylcellulose Drugs 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229920001480 hydrophilic copolymer Polymers 0.000 description 1
- 238000005213 imbibition Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- YNAVUWVOSKDBBP-UHFFFAOYSA-O morpholinium Chemical compound [H+].C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-O 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000191 poly(N-vinyl pyrrolidone) Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000002601 radiography Methods 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- 229940045105 silver iodide Drugs 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-O triethanolammonium Chemical compound OCC[NH+](CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-O 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- 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
- G03C1/04—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with macromolecular additives; with layer-forming substances
- G03C1/043—Polyalkylene oxides; Polyalkylene sulfides; Polyalkylene selenides; Polyalkylene tellurides
-
- 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
Definitions
- ABSTRACT Photographic element comprising a support and a light-sensitive silver halide emulsion layer
- the element includes in a water-permeable layer, which may be the silver halide emulsion layer, a hydrophilic colloid binder and as a surface-active agent a monoether or monoester of a polyglycol having oxyethylene units and oxypropylene units in a ratio of at least 2 oxyethylene units to l oxypropylene units, the terminal hydroxyl group of said polyglycol monoether or monoester being carboxyalkylated and the carboxyl group being in acid or salt form.
- the photographic elements do not exhibit hydrophobic inclusions which lead to repellency spots or comets'and, additionally,
- This invention relates to film-forming coating compositions comprising a hydrophilic colloid and a carboxy-alkylated polyglycol ether or ester.
- carboxyalkylated 'monoethers and monoesters of polyethylene glycol have excellent properties for use as coating aids in coating compositions comprising a hydrophilic film-forming colloid they pose a number of difficulties when used in photographic light-sensitive silver halide materials in that they may have a disadvantageous effect on the photographic characteristics of said materials. Indeed, it has been observed that in photographic paper material they give rise to yellowing and in other material produce fogging upon storage.
- coating compositions comprise a hydrophilic colloid binder material and as surface active agent a monoether or monoester of a polyglycol having oxyethylene units and oxypropylene units in a ratio of at least 2 to l, the terminal hydroxyl group of said polyisoC Hn the present invention can be represented by the following general formula:
- A represents methylene optionally substituted by an alkyl group comprising from one to five C-atoms or ethylene,
- M stands for hydrogen, an alkali metal such as sodium or potassium, ammonium or an organic ammonium e.g. diethanolammonium', triethanolammonium, morpholinium, and
- R represents an aliphatic carboxylic acyl radical or a hydrocarbon radical including substituted hydrocarbon, more particularly an aliphatic straightchain or branched-chain radical, in particular an alkyl or alkenyl radical with 6 to 24 and preferably an alkyl or alkenyl radical with 10 to 18 carbon atoms, or an alkylaryl radical, in which the aryl radical may be mononuclear or multinuclear, eg an alkylated phenyl or naphthyl radical, and in which the alkyl radical, which is a straight-chain or branched alkyl radical contains preferably 4 to 10 carbon atoms when the aryl radical is naphthyl and 6 to 14 carbon atoms when the aryl radical is phenyl,
- each of n and m stands for O to 40
- q stands for an integer such that pxq is at least 1 and at most 20,
- nXq the total number of oxyethylene units i.e. (nXq)+m being at least 5 and at most 40 and the ratio of oxyethylene units to oxypropylene units i.e. [(riXq)+m]/[pXq] being at least 2.
- the compounds-of use according to the present invention can be prepared by methods well known to those skilled in the art of organic synthesis for instance by condensation of the appropriate alcohol or acid (ROH) alternatively with ethylene oxide and isopropylene oxide (cfr. M.J. Schick Nonionic Surfactants Marcel Decker Inc., New York, 1967, Chapter 10).
- ROH alcohol or acid
- compositions containing a hydrophilic colloid binder material and a coating aid corresponding to the above general formula can be applied to dry surfaces as well as to wet surfaces and form layers that can be easily overcoated in wet as well as in dry state, the said layers being either light-sensitive layers or not.
- the coating aids according to the present invention have good anticomet properties and thus prevent the forma-' tion of repelency spots and give less rise to foaming and resulting air-bubbles than saponin and other conventional synthetic coating aids; said foaming mainly results from the presence of sulphate or sulphonate groups in the latter coating aids.
- the coating aids of use according to the present invention can also be used in combination with other coating aids e.g. coating aids that strongly reduce repellency spots but that render the layer containing. them difficult to overcoat.
- coating aids e.g. coating aids that strongly reduce repellency spots but that render the layer containing. them difficult to overcoat.
- the coating aids according to the present invention By the presence of the coating aids according to the present invention the latter disadvantage is overcome and the mentioned strong reduction of repellency spots formation is maintained.
- the coating aids according to the present invention have also favourable dispersing or emulsifying properties so that they can be used for dispersing or emulsifying substances in hydrophilic colloid compositions, which asa result of the presence of said coating aids also show improved coating characteristics.
- the coating aids according to the present invention are mainly intended for use in coating compositions comprising gelatin as hydrophilic colloid, they can also be used as coating aid for coating compositions comprising other colloidal materials or mixtures of them, e.g. hydrophilic natural colloids, modified hydrophilic natural colloids or synthetic hydrophilic polymers. More particularly these colloids may be selected of such film-forming natural or modified natural'hydrophilic colloids, as e.g., glue, casein, ze'in, hydroethylcellulose, carboxymethyl-cellulose, methylcellulose, carboxymethyl-hydroxyethylcellulose, gun arabic, sodium alginate and hydrophilic derivatives of such colloids. They may also be selected of such synthetic hydrophilic polymers as e.g.
- the compounds according to the above general formula are good coating aids for use in coating compositions as defined above either alone or in admixture with other coating aids e.g. dialkyl sulphosuccinic acid salts and salts of alkyl sulphuric acids,-salts of alkyl sulphonic I acids, salts of alkylarly polyether sulphuric acids, salts of alkylarly polyether sulphonic acids, the fluorinated coating-aids described in Belgian Patent Specification 742,680 filed Dec. 5, 1969 by Gevaert- Agfa N.V.
- coating aids according to the present invention improve the coating characteristics of coating compositions even at a concentration as low as 0.0l bt weight relative to the weight of solids. Larger concentrations, however, can also be used but generally the concentration is not higher than 5 percent by weight based on the weight of solids. in coating compositions intended for being coated as hydrophilic colloid layers in photographic silver halide materials said coating aids are generally present in amounts from 0.01 to 2 percent based on the weight of dry colloid.
- the coating aids according to the invention are particularly suitable for use in a coating composition
- a coating composition comprising gelatin as hydrophilic colloid, either as an aqueous solution of gelatin or as a photographic emulsion which ordinarily is composed of an aqueous solution of gelatin containing as the light-sensitive material therein, a silver halide such as silver bromide, silver chloride, silver iodide, or mixtures thereof or another light-sensitive substance.
- the silver halide emulsions may be coarse, medium or fine grain emulsions and may contain other added substances as sensitizing dyes, hardeners, stabilizers, pH-adjustin-g compounds, colour couplers, anti-fogging agents, development accelerators, thickening agents, developing agents, softening agents, or the like.
- the coating aids of the invention are useful in gelatin photographic emulsions, not only those which are non-optically sensitized for example X-ray emulsions, but-also in orthochromatic and panchromatic emulsions. This also includes gelatin emulsions intended for colour photography including colour radiography for example emulsions containing colour forming couplers.
- the coating aids corresponding to the above general formula and their mixtures with other coating aids are also very useful in various other types of coating compositions in which gelatin is an important constituent, for example, in gelatin coating compositions to be applied as antihalation layer to the back or front of the base in a photographic material, as protective layer, as filter-layer, as intermediate layer, as anticurling layer, etc., which layers can also contain all kinds of other ingredients such as filling agents, hardening agents, antistatic agents, anti-friction agents, or in any other type of gelatin layer, which is coated from a composition comprising an aqueous solution of gelatin, for example a gelatinreceptor layer of a blank film for producing multicolour images by imbibition printing.
- the coating compositions in accordance with our invention may be coated on a transparent support e.g. of glass, cellulose esters, polyethylene terephthalate or on a non-transparent reflecting material such as paper or an opaque cellulose ester.
- a transparent support e.g. of glass, cellulose esters, polyethylene terephthalate or on a non-transparent reflecting material such as paper or an opaque cellulose ester.
- the coating procedure may comprise any of the standard procedures employed in industry, such as roller coating, brush coating, dip-coating, spraying, using a doctor blade or an air blade to control the thickness and distribution of the coating composition.
- EXAMPLE 1 A series of 11 conventional gelatin silver chloride emulsion samples all having the same composition was prepared. To ten of these samples a certain amount of coating aid was added as listed in the following table whereas to one of these samples no coating aid at all was added. These 10 emulsions were then coated on a baryta coated paper support with grained surface whereupon the emulsion layers formed were overcoated while still wet with a protective gelatin layer containing only saponin as coating aid.
- critical speed is understood the maximum speed of the moving base' to be coated, at which the composition for forming the protective layer can still be coated.
- the layers of air carried along by the moving base are capable, at a certain speed, of preventing in large areas, contact of the material to be coated with the wet emulsion layer whereby uncoated portions remain on the moving emulsion layer.
- contact of the emulsion layer with the protective gelatin layer takes place over the entire area, the instability of the coated layer, because of the incomplete wetting of the base, does not occur and uniformity of the layer thickness is maintained.
- EXAMPLE 2 A series of fine-grain gelatino silver halide emulsions intended for being coated on a film support and all having the same composition, was prepared. To each of these emulsion samples a certain amount of coating aid or mixture of coating aids was added as listed in the following table, except for one sample to which no coating aid at all was added. After having been coated on a conventional polyethylene terephthalate film support the emulsion layers while still wet were overcoated with a protective gelatin layer. In each case the critical speed for applying the protective layers on the wet emulsion layers was determined and the number of repellency spots per sq.m. were counted for each material. The results obtained are listed in the following table.
- a coating composition comprising a light-sensitive silver halide; a hydrophilic colloid and a surface active agent wherein said surface active agent is a monoether or monoester of a polyglycol having oxyethylene units and oxypropylene units in a ratio of at least 2 oxyethylene units to 1 oxypropylene unit, the terminal hydroxyl group of said polyglycol monoether'or monoester being carboxyalkylated and the carboxyl group being in acid or salt form.
- a photographic element comprising a support and a light-sensitive silver halide emulsion layer, said element including in a water-permeable layer a hydrophilic colloid binder material and a surface active agent having a hydrophilic and hydrophobic portion, and being a monoether or monoester of a polyglycol having oxyethylene units and oxypropylene units in a ratio of at least 2 oxyethylene units to one oxypropylene unit,
- A stands for methylene optionally substituted by C C alkyl, or ethylene
- R stands for an aliphatic radical having 6 to 24 carbon atoms, or an alkyl aryl radical having from four to 14 carbon atoms in the alkyl moiety,
- M stands for hydrogen, an alkali metal atom, ammonium-or organic ammonium,
- each of n and m stands for 0 to 40
- q stands for an integer such that pXq is at least 1 and at most 20, the total number of recurring oxyethylene units being at least 5 and at most 40, and the ratio of oxyethylene units to oxypropylene units being at least 2.
- R stands for alkyl or alkenyl comprising from 10 to 18 carbon atoms or for alkylaryl in which the alkyl radical comprises from four to 14 carbon atoms.
- a photographic element according to claim 2, wherein the hydrophilic colloid binder material is gelatin.
- a photographic element according to claim 2 wherein said element comprises, in addition to said surface active compound, a surface active agent selected from the group consisting of dialkyl sulphosuccinic acid salts, salts of alkyl sulphuric acids, salts of alkylsulphonic acids, salts of alkylaryl polyether sulphuric polyether sulphonic acids.
- a surface active agent selected from the group consisting of dialkyl sulphosuccinic acid salts, salts of alkyl sulphuric acids, salts of alkylsulphonic acids, salts of alkylaryl polyether sulphuric polyether sulphonic acids.
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Abstract
Photographic element comprising a support and a light-sensitive silver halide emulsion layer is described. The element includes in a water-permeable layer, which may be the silver halide emulsion layer, a hydrophilic colloid binder and as a surfaceactive agent a monoether or monoester of a polyglycol having oxyethylene units and oxypropylene units in a ratio of at least 2 oxyethylene units to 1 oxypropylene units, the terminal hydroxyl group of said polyglycol monoether or monoester being carboxyalkylated and the carboxyl group being in acid or salt form. The photographic elements do not exhibit hydrophobic inclusions which lead to repellency spots or comets and, additionally, are resistant to yellowing upon development.
Description
[ 1 Oct. 30, 1973 I PHOTOSENSITIVE SILVER HALIDE EMULSIONS COMPRISING COATING AIDS [75] Inventors: Frans Jan Ville, Edegem; Jozef Frans Willems, Wilrijk; Paul Desire Van Pee, Edegem, all of Belgium [73] Assignee: Gevaert-AGFA, N.V., Mortsel,
Belgium [22] Filed: Nov. 24, 1970 [21] Appl. No.: 92,495
[30] Foreign Application Priority Data Dec. 31, 1969 Great Britain 63,522/69 [52] US. Cl 96/1 14.5, 96/67, 96/87 A [51] Int. Cl. G03c l/38, G03c 1/76, G030 l/78 [58] Field of Search 96/84, 114.2, 114.5, 96/87 A, 94 R, 67; 106/125 [56] References Cited UNITED STATES PATENTS 2,933,406 4/1960 Salzberg 106/125 3,003,877 10/1961 McLaughlin. 96/114.5
3,026,202 3/1962 Knox 96/ll4.5 3,038,804 6/1962 Knox.... 96/ll4.5 3,409,435 1l/l968 Seidel 96/94 3,415,649 12/1968 Nishio.. 106/125 3,514,293 5/1970 Knox 96/l14.5 3,551,152 12/1970 Mackey 96/ll4.2
1/1971 Meyer 96/87 A FOREIGN PATENTS OR APPLICATIONS 1,178,546 1/1970 Great Britain 96/1 14.5
OTHER PUBLICATIONS Nonlonic Surfactants, I. R. Schmolka, Chapter 10, pp. 304, 309-311, (1967).
Primary ExaminerNorman G. Torchin Assistant Examiner--Alfonso T. Suro Pico AttorneyBrufsky, Staas, Breiner and Halsey [57] ABSTRACT Photographic element comprising a support and a light-sensitive silver halide emulsion layer is described The element includes in a water-permeable layer, which may be the silver halide emulsion layer, a hydrophilic colloid binder and as a surface-active agent a monoether or monoester of a polyglycol having oxyethylene units and oxypropylene units in a ratio of at least 2 oxyethylene units to l oxypropylene units, the terminal hydroxyl group of said polyglycol monoether or monoester being carboxyalkylated and the carboxyl group being in acid or salt form. The photographic elements do not exhibit hydrophobic inclusions which lead to repellency spots or comets'and, additionally,
are resistant to yellowing upon development.
10 Claims, No Drawings PHOTOSENSITIVE SILVER HALIDE EMULSIONS COMPRISING COATING AIDS This invention relates to film-forming coating compositions comprising a hydrophilic colloid and a carboxy-alkylated polyglycol ether or ester.
In the application of film-forming coating compositions comprising a hydrophilic colloid to surfaces, particularly in the photographic industry, it is desirable to apply such coating compositions uniformly and at good production speeds. In many cases it is even desirable to apply such coatings 'over' other previous layers, which are either wet or dry. For this purpose the use of surface active agents as coating aids in these' hydrophilic colloid coating compositions has been widely adopted.
In the United Kingdom Patent Specification 1,178,546 it has been proposed to'use as coating aids for hydrophilic colloid coating compositions carboxyalkylated monoethers and monoesters of polyethylene glycol in acid or salt form.
Though these carboxyalkylated 'monoethers and monoesters of polyethylene glycol have excellent properties for use as coating aids in coating compositions comprising a hydrophilic film-forming colloid they pose a number of difficulties when used in photographic light-sensitive silver halide materials in that they may have a disadvantageous effect on the photographic characteristics of said materials. Indeed, it has been observed that in photographic paper material they give rise to yellowing and in other material produce fogging upon storage.
It has now been found that the disadvantageous photographic effects of the above coating aids can be reduced or eliminated while not influencing the favourable coating characteristics of these coating aids by introducing in the oxyethylene chain one or more oxypropylene units, the ratio of oxyethylene units to oxypropylene units being at least two.
Therefore, in accordance with the present invention coating compositions are provided that comprise a hydrophilic colloid binder material and as surface active agent a monoether or monoester of a polyglycol having oxyethylene units and oxypropylene units in a ratio of at least 2 to l, the terminal hydroxyl group of said polyisoC Hn the present invention can be represented by the following general formula:
A represents methylene optionally substituted by an alkyl group comprising from one to five C-atoms or ethylene,
M stands for hydrogen, an alkali metal such as sodium or potassium, ammonium or an organic ammonium e.g. diethanolammonium', triethanolammonium, morpholinium, and
R represents an aliphatic carboxylic acyl radical or a hydrocarbon radical including substituted hydrocarbon, more particularly an aliphatic straightchain or branched-chain radical, in particular an alkyl or alkenyl radical with 6 to 24 and preferably an alkyl or alkenyl radical with 10 to 18 carbon atoms, or an alkylaryl radical, in which the aryl radical may be mononuclear or multinuclear, eg an alkylated phenyl or naphthyl radical, and in which the alkyl radical, which is a straight-chain or branched alkyl radical contains preferably 4 to 10 carbon atoms when the aryl radical is naphthyl and 6 to 14 carbon atoms when the aryl radical is phenyl,
each of n and m stands for O to 40,
p stands for l to 20, and
q stands for an integer such that pxq is at least 1 and at most 20,
the total number of oxyethylene units i.e. (nXq)+m being at least 5 and at most 40 and the ratio of oxyethylene units to oxypropylene units i.e. [(riXq)+m]/[pXq] being at least 2.
The compounds-of use according to the present invention can be prepared by methods well known to those skilled in the art of organic synthesis for instance by condensation of the appropriate alcohol or acid (ROH) alternatively with ethylene oxide and isopropylene oxide (cfr. M.J. Schick Nonionic Surfactants Marcel Decker Inc., New York, 1967, Chapter 10).
whereupon the resulting polyoxyalkylene ether or ester alcohol is carboxyalkylated by means of the appropri (0 CHaCHz-)4O CHCH:(O CHzcH1-)40 CHQC O ONa lSOCsHn lSOCgHn CH z 5. lrCrSHz'I-(OCHzCHP) g0 EJHCHz-(O CHzCHz-)z0 CH2CH2) O CHzC 0 ONE.
CH3 C 3 Coating compositions containing a hydrophilic colloid binder material and a coating aid corresponding to the above general formula can be applied to dry surfaces as well as to wet surfaces and form layers that can be easily overcoated in wet as well as in dry state, the said layers being either light-sensitive layers or not. The coating aids according to the present invention have good anticomet properties and thus prevent the forma-' tion of repelency spots and give less rise to foaming and resulting air-bubbles than saponin and other conventional synthetic coating aids; said foaming mainly results from the presence of sulphate or sulphonate groups in the latter coating aids.
The coating aids of use according to the present invention can also be used in combination with other coating aids e.g. coating aids that strongly reduce repellency spots but that render the layer containing. them difficult to overcoat. By the presence of the coating aids according to the present invention the latter disadvantage is overcome and the mentioned strong reduction of repellency spots formation is maintained. Moreover, the coating aids according to the present invention have also favourable dispersing or emulsifying properties so that they can be used for dispersing or emulsifying substances in hydrophilic colloid compositions, which asa result of the presence of said coating aids also show improved coating characteristics. For instance they are suitable as dispersing agent or-emulsifying agent for substances that are to be incorporated into layers comprising a hydrophilic colloid and that would give rise to the formation of repellency spots in said layers when no compounds according to the invention were present. Other properties of the coating aids according to the present invention will appear hereinafter.
Although the coating aids according to the present invention are mainly intended for use in coating compositions comprising gelatin as hydrophilic colloid, they can also be used as coating aid for coating compositions comprising other colloidal materials or mixtures of them, e.g. hydrophilic natural colloids, modified hydrophilic natural colloids or synthetic hydrophilic polymers. More particularly these colloids may be selected of such film-forming natural or modified natural'hydrophilic colloids, as e.g., glue, casein, ze'in, hydroethylcellulose, carboxymethyl-cellulose, methylcellulose, carboxymethyl-hydroxyethylcellulose, gun arabic, sodium alginate and hydrophilic derivatives of such colloids. They may also be selected of such synthetic hydrophilic polymers as e.g. polyvinyl alcohol, poly-N-vinyl pyrrolidone, polyvinyl amine, polethylene oxide, polystyrene sulphonic acid, polyacrylic acid, and hydrophilic copolymers and derivatives of such polymers. In this connection reference is made, e.g. to United Kingdom Patent Specification l,l39,89l filed Dec. 5, 1963 by Gevaert Photo-Producten N.V. and French Patent Specification 1,507,874 filed Jan. 10, 1967 by Gevaert- Agfa N.V., which relate among others togheatand/or pressure-sensitive materials comprising a recording layer mainly consisting of a dispersion of hydrophobic thermoplastic polymer particles in a hydrophilic colloid binder.
The compounds according to the above general formula are good coating aids for use in coating compositions as defined above either alone or in admixture with other coating aids e.g. dialkyl sulphosuccinic acid salts and salts of alkyl sulphuric acids,-salts of alkyl sulphonic I acids, salts of alkylarly polyether sulphuric acids, salts of alkylarly polyether sulphonic acids, the fluorinated coating-aids described in Belgian Patent Specification 742,680 filed Dec. 5, 1969 by Gevaert- Agfa N.V. It has been found that coating aids according to the present invention improve the coating characteristics of coating compositions even at a concentration as low as 0.0l bt weight relative to the weight of solids. Larger concentrations, however, can also be used but generally the concentration is not higher than 5 percent by weight based on the weight of solids. in coating compositions intended for being coated as hydrophilic colloid layers in photographic silver halide materials said coating aids are generally present in amounts from 0.01 to 2 percent based on the weight of dry colloid.
The coating aids according to the invention are particularly suitable for use in a coating composition comprising gelatin as hydrophilic colloid, either as an aqueous solution of gelatin or as a photographic emulsion which ordinarily is composed of an aqueous solution of gelatin containing as the light-sensitive material therein, a silver halide such as silver bromide, silver chloride, silver iodide, or mixtures thereof or another light-sensitive substance. The silver halide emulsions may be coarse, medium or fine grain emulsions and may contain other added substances as sensitizing dyes, hardeners, stabilizers, pH-adjustin-g compounds, colour couplers, anti-fogging agents, development accelerators, thickening agents, developing agents, softening agents, or the like. For instance, the coating aids of the invention are useful in gelatin photographic emulsions, not only those which are non-optically sensitized for example X-ray emulsions, but-also in orthochromatic and panchromatic emulsions. This also includes gelatin emulsions intended for colour photography including colour radiography for example emulsions containing colour forming couplers.
The coating aids corresponding to the above general formula and their mixtures with other coating aids are also very useful in various other types of coating compositions in which gelatin is an important constituent, for example, in gelatin coating compositions to be applied as antihalation layer to the back or front of the base in a photographic material, as protective layer, as filter-layer, as intermediate layer, as anticurling layer, etc., which layers can also contain all kinds of other ingredients such as filling agents, hardening agents, antistatic agents, anti-friction agents, or in any other type of gelatin layer, which is coated from a composition comprising an aqueous solution of gelatin, for example a gelatinreceptor layer of a blank film for producing multicolour images by imbibition printing.
The coating compositions in accordance with our invention may be coated on a transparent support e.g. of glass, cellulose esters, polyethylene terephthalate or on a non-transparent reflecting material such as paper or an opaque cellulose ester. [t is often desirable first to coat a subbing layer to the support, this practice of subbing being well known in the art.
The coating procedure may comprise any of the standard procedures employed in industry, such as roller coating, brush coating, dip-coating, spraying, using a doctor blade or an air blade to control the thickness and distribution of the coating composition.
The following examples illustrate the present invention.
EXAMPLE 1 A series of 11 conventional gelatin silver chloride emulsion samples all having the same composition was prepared. To ten of these samples a certain amount of coating aid was added as listed in the following table whereas to one of these samples no coating aid at all was added. These 10 emulsions were then coated on a baryta coated paper support with grained surface whereupon the emulsion layers formed were overcoated while still wet with a protective gelatin layer containing only saponin as coating aid.
In each case the critical speed for applying the protective layers on the wet emulsion layers was determined and the number of repellency spots i.e. comets per sq.m were counted for each material.
By critical speed is understood the maximum speed of the moving base' to be coated, at which the composition for forming the protective layer can still be coated. Indeed, the layers of air carried along by the moving base are capable, at a certain speed, of preventing in large areas, contact of the material to be coated with the wet emulsion layer whereby uncoated portions remain on the moving emulsion layer. On decreasing the speed of coating, contact of the emulsion layer with the protective gelatin layer takes place over the entire area, the instability of the coated layer, because of the incomplete wetting of the base, does not occur and uniformity of the layer thickness is maintained.
The results obtained are listed in the following table.
Criti- Repel- Coating aid used in the emulsion and cal lenconcentration thereof in by weight of speed in cy spots dry gelatin m/min per sq.m none 4 10 0.2 of saponine 4 1 0.01 of n-C, H,,-(OCH,CH,) OCH COONa 7 1 0.025 do. 16 0 O do. 20 0 0.01 of compound 4 6 l 0.025 of compound 4 17 0 0.05 of compound 4 19 0 0.01 of compound 5 5 1 0.025 of compound 5 l5 0 0.05 of compound 5 l8 0 From the results listed in the table it appears that the critical speed obtained with coating aids according to the present invention was markedly higher than when saponin was used and was almost the same as when using compounds according to the United Kingdom Patent Specification 1,178,546. The coating aids of the invention had also the same favourable anti-comet action as the compounds of the United Kingdom Specification.
When the materials formed were developed in a standard l-phenyl-3-pyrazolidone/hydroquinone developer, stopped, rinsed, fixed and dried in the usual way and than exposed for one hour to U.V.-light, the materials comprising nC H (OCH CH OCH- COONa showed strong yellowing whereas the materials comprising compounds 4 and 5 remained unaffected.
EXAMPLE 2 A series of fine-grain gelatino silver halide emulsions intended for being coated on a film support and all having the same composition, was prepared. To each of these emulsion samples a certain amount of coating aid or mixture of coating aids was added as listed in the following table, except for one sample to which no coating aid at all was added. After having been coated on a conventional polyethylene terephthalate film support the emulsion layers while still wet were overcoated with a protective gelatin layer. In each case the critical speed for applying the protective layers on the wet emulsion layers was determined and the number of repellency spots per sq.m. were counted for each material. The results obtained are listed in the following table.
Criti- Repel- Coating aid used in the emulsion and cal lenconcentration thereof in by weight of speed in cy spots dry gelatin m/min per sq.m none 15 50 0.2 of saponine l5 15 0.01 of sodium isotetradecyl sulphate 4 2 0.01 of sodium isotetradecyl sulphate 0.01 of (OCH1CHI )BOCHQCO ONa 16 2 isoCa Hn I i 0.01 of sodium isotetradecyl sulphate 0.025 of oomcm-noomooom isoCrHn 0.01 of sodium isotetradecyl sulphate 0.05 of (OCHICHQ)BO onloooNs 40 2 lsOC'gHn 0.01 of sodium isotetradecyl sulphate 0.01 of compound I '15 3 0.01 of sodium isotetradecyl sulphate 0.025 of compound l 37 2 0.01 sodium isotetradecyl sulphate 0.05 of compound 1 39 2 0.01 of sodium isotetradecyl sulphate 0.0] of compound 2 16 4 0.01 of sodium isotetradecyl sulphate 0.025 of compound 2 37 3 0.01 of sodium isotetradecyl sulphate 0.05 of compound 2 39 1 From the results listed in the table the following can be learned. The formation of repellency spots was reduced when replacing saponin by sodium isotetradecyl magnitude as when using coating aids according to the .United Kingdom Patent Specification 1,178,546.
EXAMPLE 3 Toa conventional gelatin silver chloride emulsion were added per kg, in addition to saponin, 5 ml of a 5 percent aqueous solution of the coating air with formula:
@mcmcm-no CHzCOONa l OCgHn non:
water 800 ml anhydrous sodium sulphite 50 g anhydrous'sodium carbonate 40 g sodium hexametaphosphate 2 g l-phenyl-3-pyrazolidone 0.2g
hydroquinone 6 g potassium bromide 2 g Y The developed material was then stopped, rinsed, fixed and dried.
Upon overall exposure for one hour to U.V.-light, the exposed and developed material showed heavy yellowing whereas a material of the same composition but comprising instead of the above coating aid, 5 ml of a 5 percent aqueous solution of compound 2 showed no yellowing at all after processing and exposure to UV.- light as described above.
We claim:
1. A coating composition comprising a light-sensitive silver halide; a hydrophilic colloid and a surface active agent wherein said surface active agent is a monoether or monoester of a polyglycol having oxyethylene units and oxypropylene units in a ratio of at least 2 oxyethylene units to 1 oxypropylene unit, the terminal hydroxyl group of said polyglycol monoether'or monoester being carboxyalkylated and the carboxyl group being in acid or salt form.
2. A photographic element comprising a support and a light-sensitive silver halide emulsion layer, said element including in a water-permeable layer a hydrophilic colloid binder material and a surface active agent having a hydrophilic and hydrophobic portion, and being a monoether or monoester of a polyglycol having oxyethylene units and oxypropylene units in a ratio of at least 2 oxyethylene units to one oxypropylene unit,
acids and salts of alkylaryl the terminal hydroxyl group of said polyglycol monoether or monoester being carboxymethylated or carboxyethylated and the carboxyl group being in acid or salt form.
3. A photographic element according to claim 2, wherein said surface active agent corresponds to the formula:
wherein:
A stands for methylene optionally substituted by C C alkyl, or ethylene,
R stands for an aliphatic radical having 6 to 24 carbon atoms, or an alkyl aryl radical having from four to 14 carbon atoms in the alkyl moiety,
M stands for hydrogen, an alkali metal atom, ammonium-or organic ammonium,
each of n and m stands for 0 to 40,
p stands for 1 to 20, and
q stands for an integer such that pXq is at least 1 and at most 20, the total number of recurring oxyethylene units being at least 5 and at most 40, and the ratio of oxyethylene units to oxypropylene units being at least 2.
4. A photographic element according to claim 2, wherein R stands for alkyl or alkenyl comprising from 10 to 18 carbon atoms or for alkylaryl in which the alkyl radical comprises from four to 14 carbon atoms.
5. A photographic element according to claim 2, wherein the hydrophilic colloid binder material is gelatin.
6. A photographic element according to claim 2, wherein the said water-permeable layer is a lightsensitive silver halide emulsion layer.
7. A photographic element according to claim 2, wherein the said support is a paper support.
8. A photographic element according to claim 2, wherein the said support is a paper support and the said water-permeable layer is a light-sensitive silver halide emulsion layer.
9. A photographic element according to claim 2 wherein the surface active agent is present in said element in an amount of from 0.01 to 2 percent by weight based on the weight of the dry hydrophilic colloid.
10. A photographic element according to claim 2 wherein said element comprises, in addition to said surface active compound, a surface active agent selected from the group consisting of dialkyl sulphosuccinic acid salts, salts of alkyl sulphuric acids, salts of alkylsulphonic acids, salts of alkylaryl polyether sulphuric polyether sulphonic acids.
Claims (9)
- 2. A photographic element comprising a support and a light-sensitive silver halide emulsion layer, said element including in a water-permeable layer a hydrophilic colloid binder material and a surface active agent having a hydrophilic and hydrophobic portion, and being a monoether or monoester of a polyglycol having oxyethylene units and oxypropylene units in a ratio of at least 2 oxyethylene units to one oxypropylene unit, the terminal hydroxyl group of said polyglycol monoether or monoester being carboxymethylated or carboxyethylated and the carboxyl group being in acid or salt form.
- 3. A photographic element according to claim 2, wherein said surface active agent corresponds to the formula:
- 4. A photographic element according to claim 2, wherein R stands for alkyl or alkenyl comprising from 10 to 18 carbon atoms or for alkylaryl in which the alkyl radical comprises from four to 14 carbon atoms.
- 5. A photographic element according to claim 2, wherein the hydrophilic colloid binder material is gelatin.
- 6. A photographic element according to claim 2, wherein the said water-permeable layer is a light-sensitive silver halide emulsion layer.
- 7. A photographic element according to claim 2, wherein the said support is a paper support.
- 8. A photographic element according to claim 2, wherein the said support is a paper support and the said water-permeable layer is a light-sensitive silver halide emulsion layer.
- 9. A photographic element according to claim 2 wherein the surface active agent is present in said element in an amount of from 0.01 to 2 percent by weight based on the weight of the dry hydrophilic colloid.
- 10. A photographic element according to claim 2 wherein said element comprises, in addition to said surface active compound, a surface active agent selected from the group consisting of dialkyl sulphosuccinic acid salts, salts of alkyl sulphuric acids, salts of alkyl-sulphonic acids, salts of alkylaryl polyether sulphuric acids and salts of alkylaryl polyether sulphonic acids.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB6352269 | 1969-12-31 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3769022A true US3769022A (en) | 1973-10-30 |
Family
ID=10489093
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US00092495A Expired - Lifetime US3769022A (en) | 1969-12-31 | 1970-11-24 | Photosensitive silver halide emulsions comprising coating aids |
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|---|---|
| US (1) | US3769022A (en) |
| JP (1) | JPS4920961B1 (en) |
| BE (1) | BE760882R (en) |
| CA (1) | CA935604A (en) |
| DE (1) | DE2063713C2 (en) |
| FR (1) | FR2075007A6 (en) |
| GB (1) | GB1302880A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4073983A (en) * | 1975-04-25 | 1978-02-14 | United Chemical Corporation | Method and composition for decreasing water resistance to movement |
| US4221861A (en) * | 1978-04-06 | 1980-09-09 | The Dow Chemical Company | Backside antistatic coated film bearing a light sensitive emulsion |
| US4254208A (en) * | 1974-05-23 | 1981-03-03 | Fuji Photo Film Co., Ltd. | Photographic material |
| US4272616A (en) * | 1978-06-07 | 1981-06-09 | Fuji Photo Film Co., Ltd. | Photographic radiation-sensitive materials having improved antistatic property |
| US5011739A (en) * | 1989-10-02 | 1991-04-30 | Eastman Kodak Company | Moisture stable biasable transfer members and method for making same |
| US5156915A (en) * | 1991-11-26 | 1992-10-20 | Eastman Kodak Company | Moisture stable polyurethane biasable members |
| US5212032A (en) * | 1991-11-26 | 1993-05-18 | Eastman Kodak Company | Moisture stable polyurethane biasable transfer members |
| US5217838A (en) * | 1991-11-26 | 1993-06-08 | Eastman Kodak Company | Moisture stable biasable transfer members |
| US5250357A (en) * | 1991-11-26 | 1993-10-05 | Eastman Kodak Company | Moisture stable elastomeric polyurethane biasable transfer members |
| US9605198B2 (en) | 2011-09-15 | 2017-03-28 | Chevron U.S.A. Inc. | Mixed carbon length synthesis of primary Guerbet alcohols |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9407778D0 (en) * | 1994-04-20 | 1994-06-15 | Sandoz Ltd | Improvements in or relating to organic compounds |
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- 1970-12-11 FR FR7044890A patent/FR2075007A6/fr not_active Expired
- 1970-12-22 JP JP45117383A patent/JPS4920961B1/ja active Pending
- 1970-12-24 DE DE2063713A patent/DE2063713C2/en not_active Expired
- 1970-12-28 BE BE760882A patent/BE760882R/en active
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| US3026202A (en) * | 1958-08-07 | 1962-03-20 | Eastman Kodak Co | Gelatin coating compositions |
| US3415649A (en) * | 1963-07-01 | 1968-12-10 | Fuji Photo Film Co Ltd | Process for the production of light-sensitive material containing coating aids |
| US3409435A (en) * | 1963-08-17 | 1968-11-05 | Agfa Ag | Silver halide gelatin coating compositions containing a viscosity reducing agent |
| US3514293A (en) * | 1965-12-20 | 1970-05-26 | Eastman Kodak Co | Photographic surfactant compositions |
| GB1178546A (en) * | 1966-10-12 | 1970-01-21 | Gavaert Agfa N V | Improved Hydrophilic Coating Compositions containing Coating Aids |
| US3552972A (en) * | 1966-11-15 | 1971-01-05 | Agfa Gevaert Ag | Antistatic layer for photographic materials |
| US3551152A (en) * | 1968-06-17 | 1970-12-29 | Gaf Corp | Antistatic photographic film |
Non-Patent Citations (1)
| Title |
|---|
| Non Ionic Surfactants, I. R. Schmolka, Chapter 10, pp. 304, 309 311, (1967). * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4254208A (en) * | 1974-05-23 | 1981-03-03 | Fuji Photo Film Co., Ltd. | Photographic material |
| US4073983A (en) * | 1975-04-25 | 1978-02-14 | United Chemical Corporation | Method and composition for decreasing water resistance to movement |
| US4221861A (en) * | 1978-04-06 | 1980-09-09 | The Dow Chemical Company | Backside antistatic coated film bearing a light sensitive emulsion |
| US4272616A (en) * | 1978-06-07 | 1981-06-09 | Fuji Photo Film Co., Ltd. | Photographic radiation-sensitive materials having improved antistatic property |
| US5011739A (en) * | 1989-10-02 | 1991-04-30 | Eastman Kodak Company | Moisture stable biasable transfer members and method for making same |
| US5156915A (en) * | 1991-11-26 | 1992-10-20 | Eastman Kodak Company | Moisture stable polyurethane biasable members |
| US5212032A (en) * | 1991-11-26 | 1993-05-18 | Eastman Kodak Company | Moisture stable polyurethane biasable transfer members |
| US5217838A (en) * | 1991-11-26 | 1993-06-08 | Eastman Kodak Company | Moisture stable biasable transfer members |
| US5250357A (en) * | 1991-11-26 | 1993-10-05 | Eastman Kodak Company | Moisture stable elastomeric polyurethane biasable transfer members |
| US9605198B2 (en) | 2011-09-15 | 2017-03-28 | Chevron U.S.A. Inc. | Mixed carbon length synthesis of primary Guerbet alcohols |
| US9617464B2 (en) | 2011-09-15 | 2017-04-11 | Chevron U.S.A. Inc. | Mixed carbon length synthesis of primary guerbet alcohols |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2075007A6 (en) | 1971-10-08 |
| JPS4920961B1 (en) | 1974-05-29 |
| CA935604A (en) | 1973-10-23 |
| DE2063713C2 (en) | 1983-10-13 |
| BE760882R (en) | 1971-06-28 |
| GB1302880A (en) | 1973-01-10 |
| DE2063713A1 (en) | 1971-07-01 |
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