US3166422A - Diazotype heat development photographic paper comprising a sugar brightening agent - Google Patents
Diazotype heat development photographic paper comprising a sugar brightening agent Download PDFInfo
- Publication number
- US3166422A US3166422A US292114A US29211463A US3166422A US 3166422 A US3166422 A US 3166422A US 292114 A US292114 A US 292114A US 29211463 A US29211463 A US 29211463A US 3166422 A US3166422 A US 3166422A
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- Prior art keywords
- diazotype
- sugar
- sucrose
- acid
- compound
- Prior art date
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- Expired - Lifetime
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- 235000000346 sugar Nutrition 0.000 title description 14
- 238000005282 brightening Methods 0.000 title description 2
- 239000000463 material Substances 0.000 claims description 23
- 150000001989 diazonium salts Chemical class 0.000 claims description 11
- 238000005859 coupling reaction Methods 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 230000008878 coupling Effects 0.000 claims description 9
- 238000010168 coupling process Methods 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 230000002028 premature Effects 0.000 claims description 4
- 239000003381 stabilizer Substances 0.000 claims description 4
- GUBGYTABKSRVRQ-XLOQQCSPSA-N Alpha-Lactose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@H](O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-XLOQQCSPSA-N 0.000 claims description 3
- GUBGYTABKSRVRQ-CUHNMECISA-N D-Cellobiose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-CUHNMECISA-N 0.000 claims description 3
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 claims description 3
- 239000008101 lactose Substances 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- MUPFEKGTMRGPLJ-ZQSKZDJDSA-N raffinose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO[C@@H]2[C@@H]([C@@H](O)[C@@H](O)[C@@H](CO)O2)O)O1 MUPFEKGTMRGPLJ-ZQSKZDJDSA-N 0.000 claims description 3
- MUPFEKGTMRGPLJ-UHFFFAOYSA-N UNPD196149 Natural products OC1C(O)C(CO)OC1(CO)OC1C(O)C(O)C(O)C(COC2C(C(O)C(O)C(CO)O2)O)O1 MUPFEKGTMRGPLJ-UHFFFAOYSA-N 0.000 claims 1
- GZCGUPFRVQAUEE-KVTDHHQDSA-N aldehydo-D-mannose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)C=O GZCGUPFRVQAUEE-KVTDHHQDSA-N 0.000 claims 1
- 229930006000 Sucrose Natural products 0.000 description 18
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 18
- 239000005720 sucrose Substances 0.000 description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- 230000008569 process Effects 0.000 description 12
- 239000000203 mixture Substances 0.000 description 9
- 238000009472 formulation Methods 0.000 description 8
- 239000000975 dye Substances 0.000 description 7
- 150000008163 sugars Chemical class 0.000 description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- SAQSTQBVENFSKT-UHFFFAOYSA-M TCA-sodium Chemical compound [Na+].[O-]C(=O)C(Cl)(Cl)Cl SAQSTQBVENFSKT-UHFFFAOYSA-M 0.000 description 4
- 239000000987 azo dye Substances 0.000 description 4
- 239000012954 diazonium Substances 0.000 description 4
- 229920002689 polyvinyl acetate Polymers 0.000 description 4
- 239000011118 polyvinyl acetate Substances 0.000 description 4
- 238000006149 azo coupling reaction Methods 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- WQZGKKKJIJFFOK-QTVWNMPRSA-N D-mannopyranose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-QTVWNMPRSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 2
- 239000003906 humectant Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 description 1
- ZILVNHNSYBNLSZ-UHFFFAOYSA-N 2-(diaminomethylideneamino)guanidine Chemical class NC(N)=NNC(N)=N ZILVNHNSYBNLSZ-UHFFFAOYSA-N 0.000 description 1
- NXCOSEIUCIOFNB-UHFFFAOYSA-N 2-aminobenzenediazonium Chemical compound NC1=CC=CC=C1[N+]#N NXCOSEIUCIOFNB-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 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 1
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- WQZGKKKJIJFFOK-PHYPRBDBSA-N alpha-D-galactose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-PHYPRBDBSA-N 0.000 description 1
- ZRALSGWEFCBTJO-UHFFFAOYSA-N anhydrous guanidine Natural products NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000007850 degeneration Effects 0.000 description 1
- 150000008049 diazo compounds Chemical class 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229930182830 galactose Natural products 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- -1 guanidine compound Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- JRNGUTKWMSBIBF-UHFFFAOYSA-N naphthalene-2,3-diol Chemical compound C1=CC=C2C=C(O)C(O)=CC2=C1 JRNGUTKWMSBIBF-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- WFQYHKXNZVCNDO-UHFFFAOYSA-M sodium 2,2,2-trichloroacetate 2,2,2-trichloroacetic acid Chemical compound [Na+].OC(=O)C(Cl)(Cl)Cl.[O-]C(=O)C(Cl)(Cl)Cl WFQYHKXNZVCNDO-UHFFFAOYSA-M 0.000 description 1
- JFXDYPLHFRYDJD-UHFFFAOYSA-M sodium;6,7-dihydroxynaphthalene-2-sulfonate Chemical compound [Na+].C1=C(S([O-])(=O)=O)C=C2C=C(O)C(O)=CC2=C1 JFXDYPLHFRYDJD-UHFFFAOYSA-M 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 229940066528 trichloroacetate Drugs 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
- G03C1/52—Compositions containing diazo compounds as photosensitive substances
- G03C1/61—Compositions containing diazo compounds as photosensitive substances with non-macromolecular additives
Definitions
- the present invention relates to a diazotype heat de-j It relates velopment photographic paper and process. more particularly to a two-component diazotypej photographic process and the light-sensitive diazotype photoprinting material employed therein which is capable of producing bright and distinct dye images.
- the invention makes use of a combination of a lightsensitive diazonium compound and an azo coupling component contained in a coating, which couple to produce an azo dye.
- the invention moreover, involves the use of heat developable diazotype and coupler-materials which are physically and chemically stable during ordinary storage and which also have other unique and desirable properties. It involves, more particularly, an improvement in brightness of the dye image, as compared with prior heat development processes.
- the diazotype process is well known. It involves exposure to actinic light under an original having an opaque pattern on a translucent background of sheet material bearing a light-sensitive diazonium compound, and in two-component material-also an azo coupling component, stabilized with an acid against premature coupling, whereby the diazonium compound is 3,156,422 Patented Jan. 19, 1965 biguanidine salt of a diazo compound which would decompose underthe influence of heat to yield ammonia w as a developing agent.
- US. Patent 2,178,771 separate layers were proposed and development by use of steam was suggested.
- Various other patents have suggested other processes involving heat.
- the diazonium salts and couplers are normally applied in such away, e.g., in combination with an acid stabilizer, so that theycannot react until the pH of the system is altered, eg, by application of a basic compound.
- a basic compound e.g., The latter may be generated or evolved by heating.
- Such a compound might be one which, when heated, gives rise to an alkaline environment, as in the case of the guanidine compound of the patent mentioned above. In most cases, application of heat produces a dull image.
- alkaline generating agents such as urea or trichlor-oacetic acid-sodium trichloroacetate in an acidic system for coupling has been proposed in the prior art.
- a process which has enjoyed moderate success is a dry diazo process.
- the dry process of the prior art using two-component diazotype materials commonly makes use of aqueous ammonia at an elevated temperature to promote the coupling reaction.
- the ammonia is applied in such a manner as to cause the two reactive materials on the supporting sheet to react andthereby to form a water insoluble azo dye.
- This process has the obvious disadvantages that the odor of ammonia is involved and that the handling of ammonia, usually in the form of aqueous ammonia solutions, is necessary. Also, there are complications in the apparatus necessitated by the use of ammonia. Hence the process, and the necessary equipment, are not always suitable for use, for example, in ofiice reproduction systems where the diazo process otherwise has certain advantages.
- This complex system is preferably replaced by a single base generating compound such as an alkali metal-, 'ammoniumor nitrogen base salt of trichloroacetic acid.
- a single base generating compound such as an alkali metal-, 'ammoniumor nitrogen base salt of trichloroacetic acid.
- an object of the present invention is to prevent this undesirable loss of brightness in the heat developed dye image.
- This is accomplished by adding a sugar of the class consisting of sucrose, lactose, cellobiose, rafli nose and mannose or mixtures thereof to the dye forming reactant materials.
- these sugars have been found effective to prevent loss of brightness, while other common sugars such as glucose, fructose, maltose and galactose were found to have the opposite elfectreducing the image density.
- humectants such as glycol and glycerin will, to some extent, reduce or eliminate the loss of dye brightness.
- materials containing these humectants have poor shelf life.
- sugar such as sucrose may be added to the formulation to improve the brightness without adversely affecting shelf life.
- sucrose or of the other sugars specified above can be varied somewhat but is usually within the range of 5 to 20 times the Weight of the diazonium salt in the formulation, or 2 to 7 times the weight of the azo coupler.
- the formulations which include an acid stabilizer such as citric acid so as to prevent premature coupling, and sucrose or equivalent to insure Citric acid gm q. brightness, oifer a number of unique advantages.
- an acid stabilizer such as citric acid so as to prevent premature coupling
- sucrose or equivalent to insure Citric acid gm q. brightness, oifer a number of unique advantages.
- Example 1 Water ml 6 0. N ethyl N 2 hydroxyethyl p aminobenzenediazonium chlorozincate gm 1.0 2,3-dihydroxynaphthalene-6-sodium sulfonate gm 3.0 Sucrose gm Shawinigan RS-4326 (a low viscosity grade of polyvinyl alcohol) gm 5 Sodium trichloroacetate gm 4 National Resyn 1006 (a polyvinyl acetate emulsion) ml 5 Silica (average particle size: 3-6 microns) gm 4 Water to 100 ml.
- Onyx Resin Xyno X99 (an aqueous polyvinyl acetate emulsion containing 60% polyvinylacetate) ml Water to 100 ml.
- Dried material was processed to form a copy by heat development in the same manner as described in Example 1.
- the material containing sucrose resulted in a substantially brighter image than that obtained with material from which sucrose was omitted.
- Example 3 The procedure of Example 2 was repeated except that sucrose was removed from Part II solution and added to Part 1 solution. The results were essentially the same. Hence, it does not appear to be particularly critical whether the sucrose is added to the diazonium layer or to 'the coupling layer, when separate coatings or layers chosen from any compounds which have aneutral or acid reaction at normal temperatures provided the substance chosen also gives rise to an alkaline environment upon the application of heat at temperatures of the. order of 100 to 200 C., alkalimetal (-Na, K),-am'monium and nitrogen base trichloroacetates meet these requirements quite satisfactorily and are preferred for the purposes of this invention. a w
- Thedegree of heat required to develop the photograph Will.,depend somewhat on the particular ingredients in the coating material or materials. it should be within a temperature range of to 200 C. and preferably .120 C., and should be applied only for a short period of time, ordinarily of the order of seconds or fractions thereof.
- the sucrose and other sugars named above enhance the brightness of single as well as double layer materials as disclosed in the examples.
- the mechanisrn by which the addition of the sucrose and other sugars produce brightness in the azo dye images is not certain, but it may be that, due to the application of heat, the sugars themselves partially break down and generate moisture, which tends to replace that lost in the paper. In any case, the improvement in the brightness of the image produced by use of sucrose and the other sugars is substantial. Prints made with sucrose are such superior to those produced without it.
- a two-component diazotype photo-printing material having on the surface of a supporting sheet a lightsensitive diazoniurn compound, an azo coupler, an acid stabilizer against premature coupling, a neutral to acid compound which on heating to a temperature of 100 to 200 C. produces an alkaline reaction, and a sugar selected from the class consisting of sucrose, lactose, cellobiose, mannose and raflinose.
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- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
- Heat Sensitive Colour Forming Recording (AREA)
Description
United States Patent 3,166,422 DIAZOTYPE HEAT DEVELQPMENT PHUTO- GRAPHIC PAPER COMPRISILNG A SUGAR ,BRIGHTENING AGENT Q John Joseph McKinney, Binghamton, and Bernard I. Helper-in, Glen Aubrey, N.Y., assignors to General Auiiine & Film Corporation, New York, N.Y., a corporation of Delaware. p t No Drawing. Filed July 1, 1963, Ser. No. 292,114
, 6 Claiuns. (Cl. 96-75) The present invention relates to a diazotype heat de-j It relates velopment photographic paper and process. more particularly to a two-component diazotypej photographic process and the light-sensitive diazotype photoprinting material employed therein which is capable of producing bright and distinct dye images.
The invention makes use of a combination of a lightsensitive diazonium compound and an azo coupling component contained in a coating, which couple to produce an azo dye. The invention, moreover, involves the use of heat developable diazotype and coupler-materials which are physically and chemically stable during ordinary storage and which also have other unique and desirable properties. It involves, more particularly, an improvement in brightness of the dye image, as compared with prior heat development processes.
In the prior art, numerous proposals have been made for various modifications of the original diazotype photographic process. Basically the diazotype process is well known. It involves exposure to actinic light under an original having an opaque pattern on a translucent background of sheet material bearing a light-sensitive diazonium compound, and in two-component material-also an azo coupling component, stabilized with an acid against premature coupling, whereby the diazonium compound is 3,156,422 Patented Jan. 19, 1965 biguanidine salt of a diazo compound which would decompose underthe influence of heat to yield ammonia w as a developing agent. In US. Patent 2,178,771 separate layers were proposed and development by use of steam was suggested. Various other patents have suggested other processes involving heat.
The diazonium salts and couplers are normally applied in such away, e.g., in combination with an acid stabilizer, so that theycannot react until the pH of the system is altered, eg, by application of a basic compound. The latter may be generated or evolved by heating. Such a compound might be one which, when heated, gives rise to an alkaline environment, as in the case of the guanidine compound of the patent mentioned above. In most cases, application of heat produces a dull image.
The use of alkaline generating agents, such as urea or trichlor-oacetic acid-sodium trichloroacetate in an acidic system for coupling has been proposed in the prior art.
destroyed in the light-struck areas, and developing by alkaline treatment to cause coupling of the residual diazonium compound and coupling component forming, an azo dye image in the areas protected by the opaque pattern.
A process which has enjoyed moderate success is a dry diazo process. The dry process of the prior art using two-component diazotype materials commonly makes use of aqueous ammonia at an elevated temperature to promote the coupling reaction. The ammonia is applied in such a manner as to cause the two reactive materials on the supporting sheet to react andthereby to form a water insoluble azo dye. This process has the obvious disadvantages that the odor of ammonia is involved and that the handling of ammonia, usually in the form of aqueous ammonia solutions, is necessary. Also, there are complications in the apparatus necessitated by the use of ammonia. Hence the process, and the necessary equipment, are not always suitable for use, for example, in ofiice reproduction systems where the diazo process otherwise has certain advantages.
The dry developing process, using ammonia, has several practical objections. It requires the purchase and use of a relatively complex development apparatus unit. As a result, diazotype reproducing machines tend to be relatively expensive and thus less competitive economically with other systems. This is particularly true for the relatively simple copying operationswhere convenience and freedom from operating diificulties are so important.
Numerous attempts have been made in the prior art to obviate some of the deficiencies described above. Thus, it has been proposed to prepare and apply the individual Reaction takes place on heating. However, urea decomposes slowly at moderate storage temperatures and even at normal room temperature. Furthermore, relatively large amounts of urea are required for satisfactory development. It is diflicult to store materials of this type and maintain proper quality over moderate periods of time. The trichloroacetic acid-sodium trichloroacetate systemhas not been satisfactory, in general, because the excess trichloroacetic acid usually causes severe degeneration of the paper. In addition, the sodium trichloroacetate itself tends to cause the diazonium salt to decompose prematurely. This complex system is preferably replaced by a single base generating compound such as an alkali metal-, 'ammoniumor nitrogen base salt of trichloroacetic acid. In the aforesaid procedures, the degree of heat required is often such as to drive the normal paper moisture out of the sheet and to cause partial decomposition, concurrcntly with coupling, of the light-sensitive diazonium compound. The loss of this moisture and said decomposition causes formation of dyes that are dull.
Hence, an object of the present invention is to prevent this undesirable loss of brightness in the heat developed dye image. This is accomplished by adding a sugar of the class consisting of sucrose, lactose, cellobiose, rafli nose and mannose or mixtures thereof to the dye forming reactant materials. Surprisingly, these sugars have been found effective to prevent loss of brightness, while other common sugars such as glucose, fructose, maltose and galactose were found to have the opposite elfectreducing the image density. I
The addition of humectants such as glycol and glycerin will, to some extent, reduce or eliminate the loss of dye brightness. However, materials containing these humectants have poor shelf life. According to the present invention sugar such as sucrose may be added to the formulation to improve the brightness without adversely affecting shelf life.
The amount of sucrose or of the other sugars specified above can be varied somewhat but is usually within the range of 5 to 20 times the Weight of the diazonium salt in the formulation, or 2 to 7 times the weight of the azo coupler.
In other respects, the formulations, which include an acid stabilizer such as citric acid so as to prevent premature coupling, and sucrose or equivalent to insure Citric acid gm q. brightness, oifer a number of unique advantages. Such formulations will be illustrated by the examples which follow:
Example 1 Water ml 6 0. N ethyl N 2 hydroxyethyl p aminobenzenediazonium chlorozincate gm 1.0 2,3-dihydroxynaphthalene-6-sodium sulfonate gm 3.0 Sucrose gm Shawinigan RS-4326 (a low viscosity grade of polyvinyl alcohol) gm 5 Sodium trichloroacetate gm 4 National Resyn 1006 (a polyvinyl acetate emulsion) ml 5 Silica (average particle size: 3-6 microns) gm 4 Water to 100 ml.
The above formulation and a formulation identical to the abovebut-not containing sucrose, were. coated on paper by means of conventional equipment. The dried material was exposed to light under an opaque image in the same way as conventional diazotype material, but
developed by passing the sheet over a roller heated to 300 F..350 F. Prints made from material containing sucrose showed superior dye brightness to prints made from Shawinigan RS-4326 (a aqueous solution of a low viscosity grade of polyvinyl alcohol) ml 20 NationalResyn 1006 (a polyvinyl acetate emulsion) ml 5 Water to 100 ml.
The above formulation was coated and dried on conventional equipment. This material was then coated with the following:
Part 2:
Water ml ,60 Sucrose gm-.. 10 2,3 dihydroxynaphthalene 6 -.sodium sulfonate gm 3.0 Sodium trichloroacetate gm 3.0
Onyx Resin Xyno X99 (an aqueous polyvinyl acetate emulsion containing 60% polyvinylacetate) ml Water to 100 ml.
A formulation the same as the above but from which sucrose was omitted was also coated on the Part I'layer.
Dried material was processed to form a copy by heat development in the same manner as described in Example 1. The material containing sucrose resulted in a substantially brighter image than that obtained with material from which sucrose was omitted.
Example 3 The procedure of Example 2 was repeated except that sucrose was removed from Part II solution and added to Part 1 solution. The results were essentially the same. Hence, it does not appear to be particularly critical whether the sucrose is added to the diazonium layer or to 'the coupling layer, when separate coatings or layers chosen from any compounds which have aneutral or acid reaction at normal temperatures provided the substance chosen also gives rise to an alkaline environment upon the application of heat at temperatures of the. order of 100 to 200 C., alkalimetal (-Na, K),-am'monium and nitrogen base trichloroacetates meet these requirements quite satisfactorily and are preferred for the purposes of this invention. a w
I Thedegree of heat required to develop the photograph Will.,depend somewhat on the particular ingredients in the coating material or materials. it should be within a temperature range of to 200 C. and preferably .120 C., and should be applied only for a short period of time, ordinarily of the order of seconds or fractions thereof. The sucrose and other sugars named above, enhance the brightness of single as well as double layer materials as disclosed in the examples. The mechanisrn by which the addition of the sucrose and other sugars produce brightness in the azo dye images is not certain, but it may be that, due to the application of heat, the sugars themselves partially break down and generate moisture, which tends to replace that lost in the paper. In any case, the improvement in the brightness of the image produced by use of sucrose and the other sugars is substantial. Prints made with sucrose are such superior to those produced without it.
It will be obvious that a number of variations may be made in the invention as will readily occur to those skilled in the art. It is intended by the claims which follow to cover such improvements as far as the prior art permits.
We claim:
1. A two-component diazotype photo-printing material having on the surface of a supporting sheet a lightsensitive diazoniurn compound, an azo coupler, an acid stabilizer against premature coupling, a neutral to acid compound which on heating to a temperature of 100 to 200 C. produces an alkaline reaction, and a sugar selected from the class consisting of sucrose, lactose, cellobiose, mannose and raflinose.
2. A two-component diazotype material as defined in claim l-wherein the'sugar is present in an amount from 5-20 times the quantity of said diazonium compound.
3. Atwo-component diazotype photo-printing material as defined in claim 1 wherein the sugar is present in an amount from 2 to 7 times the quantity of said azo coupling component.
No references cited.
Generally speaking,
Claims (2)
1. A TWO-COMPONENT DIAZOTYPE PHOTO-PRINTING MATERIAL HAVING ON THE SURFACE OF A SUPPORTING SHEET A LIGHTSENSITIVE DIAZONIUM COMPOUND, AN AZO COUPLER, AN ACID STABILIZER AGAINST PREMATURE COUPLING, A NEUTRAL TO ACID COMPOUND WHICH ON HEATING TO A TEMPERATURE OF 100 TO 200*C. PRODUCES AN ALKALINE REACTION, AND A SUGARD SELECTED FROM THE CLASS CONSISTING OF SURCROSE, LACTOSE, CELLOBIOSE, MANNOSE AND RAFFINOSE.
5. A DIAZOTYPE PHOTO-PRINTING MATERIAL AS DEFINED IN CLAIM 1 WHEREIN SAID DIAZONIUM COMPOUND AND SAID ACID TO NEUTRAL COMPOUNDS ARE CONTAINED IN SEPARATE BUT SUPERPOSED CONTIGUOUS LAYERS.
Priority Applications (10)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US284364A US3326686A (en) | 1963-05-31 | 1963-05-31 | Light-sensitive two-component diazotype materials adapted for heat development |
US292098A US3298834A (en) | 1963-05-31 | 1963-07-01 | Diazotype photoprinting material susceptible to thermal development |
US292097A US3301679A (en) | 1963-05-31 | 1963-07-01 | Two-component diazotype light-sensitive photoprinting material susceptible to thermal development |
US292066A US3294534A (en) | 1963-05-31 | 1963-07-01 | Diazotype photoprinting material susceptible to thermal development |
US292114A US3166422A (en) | 1963-05-31 | 1963-07-01 | Diazotype heat development photographic paper comprising a sugar brightening agent |
US292115A US3255011A (en) | 1963-05-31 | 1963-07-01 | Two-component diazotype photoprinting material susceptible to thermal development |
GB21014/64A GB1063132A (en) | 1963-05-31 | 1964-05-21 | Improvements in or relating to light-sensitive two-component diazotype materials adapted for heat development |
NL6406013A NL6406013A (en) | 1963-05-31 | 1964-05-28 | |
FR976481A FR1405427A (en) | 1963-05-31 | 1964-05-29 | Two-component diazo-type materials, photosensitive for thermal development |
BE648593D BE648593A (en) | 1963-05-31 | 1964-05-29 |
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US284364A US3326686A (en) | 1963-05-31 | 1963-05-31 | Light-sensitive two-component diazotype materials adapted for heat development |
US292098A US3298834A (en) | 1963-05-31 | 1963-07-01 | Diazotype photoprinting material susceptible to thermal development |
US292097A US3301679A (en) | 1963-05-31 | 1963-07-01 | Two-component diazotype light-sensitive photoprinting material susceptible to thermal development |
US292066A US3294534A (en) | 1963-05-31 | 1963-07-01 | Diazotype photoprinting material susceptible to thermal development |
US292114A US3166422A (en) | 1963-05-31 | 1963-07-01 | Diazotype heat development photographic paper comprising a sugar brightening agent |
US292115A US3255011A (en) | 1963-05-31 | 1963-07-01 | Two-component diazotype photoprinting material susceptible to thermal development |
Publications (1)
Publication Number | Publication Date |
---|---|
US3166422A true US3166422A (en) | 1965-01-19 |
Family
ID=27559573
Family Applications (6)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US284364A Expired - Lifetime US3326686A (en) | 1963-05-31 | 1963-05-31 | Light-sensitive two-component diazotype materials adapted for heat development |
US292066A Expired - Lifetime US3294534A (en) | 1963-05-31 | 1963-07-01 | Diazotype photoprinting material susceptible to thermal development |
US292097A Expired - Lifetime US3301679A (en) | 1963-05-31 | 1963-07-01 | Two-component diazotype light-sensitive photoprinting material susceptible to thermal development |
US292114A Expired - Lifetime US3166422A (en) | 1963-05-31 | 1963-07-01 | Diazotype heat development photographic paper comprising a sugar brightening agent |
US292098A Expired - Lifetime US3298834A (en) | 1963-05-31 | 1963-07-01 | Diazotype photoprinting material susceptible to thermal development |
US292115A Expired - Lifetime US3255011A (en) | 1963-05-31 | 1963-07-01 | Two-component diazotype photoprinting material susceptible to thermal development |
Family Applications Before (3)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US284364A Expired - Lifetime US3326686A (en) | 1963-05-31 | 1963-05-31 | Light-sensitive two-component diazotype materials adapted for heat development |
US292066A Expired - Lifetime US3294534A (en) | 1963-05-31 | 1963-07-01 | Diazotype photoprinting material susceptible to thermal development |
US292097A Expired - Lifetime US3301679A (en) | 1963-05-31 | 1963-07-01 | Two-component diazotype light-sensitive photoprinting material susceptible to thermal development |
Family Applications After (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US292098A Expired - Lifetime US3298834A (en) | 1963-05-31 | 1963-07-01 | Diazotype photoprinting material susceptible to thermal development |
US292115A Expired - Lifetime US3255011A (en) | 1963-05-31 | 1963-07-01 | Two-component diazotype photoprinting material susceptible to thermal development |
Country Status (4)
Country | Link |
---|---|
US (6) | US3326686A (en) |
BE (1) | BE648593A (en) |
GB (1) | GB1063132A (en) |
NL (1) | NL6406013A (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3300471A (en) * | 1964-01-02 | 1967-01-24 | Universal Oil Prod Co | p-(nu-cyanoalkyl-nu-hydrocarbylamino)-benzenediazonium chlorides |
US3380830A (en) * | 1963-09-24 | 1968-04-30 | Bauchet & Cie | Heat developable diazo photocopying sheet |
US3420666A (en) * | 1964-10-15 | 1969-01-07 | Gaf Corp | Two-component heat developing diazotypes |
US3525618A (en) * | 1964-12-04 | 1970-08-25 | Geigy Ag J R | Diazotype film materials |
Families Citing this family (30)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3536490A (en) * | 1964-04-28 | 1970-10-27 | Pitney Bowes Inc | Novel diazotype copying process |
US3408192A (en) * | 1964-06-10 | 1968-10-29 | Ibm | Light-sensitive diazotype compositions and elements |
US3389995A (en) * | 1964-09-15 | 1968-06-25 | Gen Aniline & Film Corp | Two-component heat developable diazotypes containing amidine compounds |
US3389996A (en) * | 1964-10-15 | 1968-06-25 | Gen Aniline & Film Corp | Two-component heat developable diazotypes |
US3431109A (en) * | 1964-10-16 | 1969-03-04 | Addressograph Multigraph | Heat sensitive diazotype materials |
USB417241I5 (en) * | 1964-12-09 | |||
US3406072A (en) * | 1964-12-21 | 1968-10-15 | Gaf Corp | One-component diazotypes |
US3409455A (en) * | 1965-01-04 | 1968-11-05 | Gaf Corp | Process of reproduction on benzene diazonium fluoborate sheet by heat exposure |
US3379531A (en) * | 1965-03-30 | 1968-04-23 | Gen Aniline & Film Corp | Two-component heat developing diazotypes |
DE1572155A1 (en) * | 1965-08-10 | 1970-01-02 | Dr Eduard Roell | Light or radiation sensitive material and process for its production |
US3522048A (en) * | 1965-12-09 | 1970-07-28 | Gaf Corp | Two-component heat developing diazotypes |
US3529964A (en) * | 1966-01-14 | 1970-09-22 | L L Ridgway Enterprises Inc | Heat developable diazo compositions and diazotype reproduction media |
NL136527C (en) * | 1966-11-07 | |||
US3539345A (en) * | 1967-02-01 | 1970-11-10 | Gaf Corp | Thermal diazotype papers |
NL6800539A (en) * | 1968-01-12 | 1969-07-15 | ||
GB1292607A (en) * | 1968-12-28 | 1972-10-11 | Ricoh Kk | Improvements in and relating to heat-developable light-sensitive material |
US3779758A (en) * | 1969-03-25 | 1973-12-18 | Photocircuits Corp | Photosensitive process for producing printed circuits employing electroless deposition |
JPS4832722B1 (en) * | 1969-09-01 | 1973-10-08 | ||
US3793030A (en) * | 1971-09-02 | 1974-02-19 | Ricoh Kk | Process for producing diazotype light-sensitive material |
US3900324A (en) * | 1972-06-25 | 1975-08-19 | Ozalid Co Ltd | Treatment of synthetic polyester film products |
GB1488005A (en) * | 1974-01-25 | 1977-10-05 | Ici Ltd | Diazotype materials |
US4168171A (en) * | 1977-08-05 | 1979-09-18 | Minnesota Mining And Manufacturing Company | Light-sensitive thermal developable diazotype sheets with imidazoles |
US4230789A (en) * | 1978-03-13 | 1980-10-28 | Minnesota Mining And Manufacturing Company | Thermal diazotype sheets |
FR2455303A1 (en) * | 1979-04-24 | 1980-11-21 | Rhone Poulenc Syst | PROCESS FOR THE MANUFACTURE OF A INVIOLABLE IDENTIFICATION CARD COMPRISING PHOTOGRAPHS AND CARD OBTAINED ACCORDING TO THIS PROCESS |
FR2470984B1 (en) * | 1979-11-28 | 1986-06-13 | Schaeffer Andre | DIAZOTYPE MATERIAL DEVELOPABLE BY VAPOR, WATER OR HEAT |
BR8107605A (en) * | 1981-11-23 | 1983-07-05 | Oce Nederland Bv | DIAZOTYPE MATERIAL |
JPS5898729A (en) * | 1981-12-08 | 1983-06-11 | Ricoh Co Ltd | Production of heat developing type diazo copying material |
US4478926A (en) * | 1981-12-28 | 1984-10-23 | Andrews Paper & Chemical Co., Inc. | Zinc sulfonates and their use in diazotypy |
JPS58143336A (en) * | 1982-02-19 | 1983-08-25 | Ricoh Co Ltd | Thermodevelopable type diazo copying material |
US4508808A (en) * | 1982-11-12 | 1985-04-02 | Xidex Corporation | Method of using diazotype photographic materials with preexposure treatment to form uniform sites of refractive index change |
Family Cites Families (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB816601A (en) * | 1954-07-09 | 1959-07-15 | Arnold Tanenbaum | Improvements in or relating to diazotype processes |
FR750080A (en) * | 1932-04-27 | 1933-08-03 | Process for preparing light-sensitive layers | |
NL71256C (en) * | 1948-10-01 | |||
US2653091A (en) * | 1950-01-31 | 1953-09-22 | Rca Corp | Photographic diazotype composition and heat development thereof |
US2727820A (en) * | 1952-04-29 | 1955-12-20 | Gen Aniline & Film Corp | Light-sensitive diazotype layers containing carboxamides |
US2807545A (en) * | 1952-07-18 | 1957-09-24 | Dick Co Ab | Process of applying a diazotype photoprinting material to a base and the resultant article |
US2732299A (en) * | 1952-07-22 | 1956-01-24 | Light sensitive | |
GB815005A (en) * | 1957-07-03 | 1959-06-17 | Ilford Ltd | Improvements in or relating to radiation-sensitive diazotype materials |
GB861601A (en) * | 1957-07-26 | 1961-02-22 | Napier & Son Ltd | Control mechanism for aircraft power plants comprising a gas turbine engine driving a propeller |
NL279582A (en) * | 1958-07-03 | |||
FR1255950A (en) * | 1959-11-23 | 1961-03-17 | Bauchet Et Cie Ets | New heat-developable diazotype product |
NL258232A (en) * | 1959-11-23 | |||
US3220846A (en) * | 1960-06-27 | 1965-11-30 | Eastman Kodak Co | Use of salts of readily decarboxylated acids in thermography, photography, photothermography and thermophotography |
US3102812A (en) * | 1960-11-16 | 1963-09-03 | Gen Aniline & Film Corp | Stabilizers for one-component diazotype materials |
BE609912A (en) * | 1961-11-02 | |||
US3157503A (en) * | 1963-03-19 | 1964-11-17 | Keuffel & Esser Co | Diazotype reproduction materials |
-
1963
- 1963-05-31 US US284364A patent/US3326686A/en not_active Expired - Lifetime
- 1963-07-01 US US292066A patent/US3294534A/en not_active Expired - Lifetime
- 1963-07-01 US US292097A patent/US3301679A/en not_active Expired - Lifetime
- 1963-07-01 US US292114A patent/US3166422A/en not_active Expired - Lifetime
- 1963-07-01 US US292098A patent/US3298834A/en not_active Expired - Lifetime
- 1963-07-01 US US292115A patent/US3255011A/en not_active Expired - Lifetime
-
1964
- 1964-05-21 GB GB21014/64A patent/GB1063132A/en not_active Expired
- 1964-05-28 NL NL6406013A patent/NL6406013A/xx unknown
- 1964-05-29 BE BE648593D patent/BE648593A/xx unknown
Non-Patent Citations (1)
Title |
---|
None * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3380830A (en) * | 1963-09-24 | 1968-04-30 | Bauchet & Cie | Heat developable diazo photocopying sheet |
US3300471A (en) * | 1964-01-02 | 1967-01-24 | Universal Oil Prod Co | p-(nu-cyanoalkyl-nu-hydrocarbylamino)-benzenediazonium chlorides |
US3420666A (en) * | 1964-10-15 | 1969-01-07 | Gaf Corp | Two-component heat developing diazotypes |
US3525618A (en) * | 1964-12-04 | 1970-08-25 | Geigy Ag J R | Diazotype film materials |
Also Published As
Publication number | Publication date |
---|---|
BE648593A (en) | 1964-09-16 |
NL6406013A (en) | 1964-12-01 |
US3294534A (en) | 1966-12-27 |
US3298834A (en) | 1967-01-17 |
US3255011A (en) | 1966-06-07 |
US3326686A (en) | 1967-06-20 |
GB1063132A (en) | 1967-03-30 |
US3301679A (en) | 1967-01-31 |
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Owner name: R Q O HOLDING COMPANY INC 111 WEST 2ND ST JAMESTOW Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:GAF CORPORATION;REEL/FRAME:004006/0585 Effective date: 19820526 Owner name: R Q O HOLDING COMPANY INC, NEW YORK Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:GAF CORPORATION;REEL/FRAME:004006/0585 Effective date: 19820526 |