US3236646A - Copying material for the photomechanical production of printing plates especially planographic and offset printing plates - Google Patents
Copying material for the photomechanical production of printing plates especially planographic and offset printing plates Download PDFInfo
- Publication number
- US3236646A US3236646A US167910A US16791062A US3236646A US 3236646 A US3236646 A US 3236646A US 167910 A US167910 A US 167910A US 16791062 A US16791062 A US 16791062A US 3236646 A US3236646 A US 3236646A
- Authority
- US
- United States
- Prior art keywords
- acid
- diphenylamine
- diazonium
- parts
- condensation product
- 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
- 238000007639 printing Methods 0.000 title claims description 60
- 239000000463 material Substances 0.000 title description 39
- 238000004519 manufacturing process Methods 0.000 title description 8
- 238000007645 offset printing Methods 0.000 title description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 156
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 114
- 239000007859 condensation product Substances 0.000 claims description 109
- 239000012954 diazonium Substances 0.000 claims description 88
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 65
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 52
- 239000002253 acid Substances 0.000 claims description 47
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 43
- 238000000034 method Methods 0.000 claims description 34
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 28
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 21
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 13
- 235000011007 phosphoric acid Nutrition 0.000 description 57
- 239000000243 solution Substances 0.000 description 42
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 39
- 239000000203 mixture Substances 0.000 description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 35
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 31
- 229910019142 PO4 Inorganic materials 0.000 description 30
- 238000009833 condensation Methods 0.000 description 29
- 230000005494 condensation Effects 0.000 description 29
- 235000021317 phosphate Nutrition 0.000 description 28
- 238000000576 coating method Methods 0.000 description 26
- 150000003839 salts Chemical class 0.000 description 26
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 25
- 229910052782 aluminium Inorganic materials 0.000 description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical group [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 description 24
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 24
- 239000011248 coating agent Substances 0.000 description 23
- 239000010452 phosphate Substances 0.000 description 20
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 17
- 239000002585 base Substances 0.000 description 17
- 239000011888 foil Substances 0.000 description 17
- 229910052751 metal Inorganic materials 0.000 description 17
- 239000002184 metal Substances 0.000 description 17
- 230000007935 neutral effect Effects 0.000 description 14
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 12
- 239000000123 paper Substances 0.000 description 11
- 229930040373 Paraformaldehyde Natural products 0.000 description 10
- 229920002866 paraformaldehyde Polymers 0.000 description 10
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 8
- 150000001805 chlorine compounds Chemical class 0.000 description 8
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- -1 diazoamino compounds Chemical class 0.000 description 7
- 150000001989 diazonium salts Chemical class 0.000 description 7
- 244000215068 Acacia senegal Species 0.000 description 6
- 229920000084 Gum arabic Polymers 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000000205 acacia gum Substances 0.000 description 6
- 235000010489 acacia gum Nutrition 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 6
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical group C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 5
- 239000004922 lacquer Substances 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 4
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 150000004820 halides Chemical class 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 206010034960 Photophobia Diseases 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910001626 barium chloride Inorganic materials 0.000 description 3
- 239000012876 carrier material Substances 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 3
- 208000013469 light sensitivity Diseases 0.000 description 3
- 229910001507 metal halide Inorganic materials 0.000 description 3
- 150000005309 metal halides Chemical class 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Chemical group 0.000 description 2
- 150000001649 bromium compounds Chemical class 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229920002301 cellulose acetate Polymers 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 150000008049 diazo compounds Chemical class 0.000 description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- VFRSADQPWYCXDG-LEUCUCNGSA-N ethyl (2s,5s)-5-methylpyrrolidine-2-carboxylate;2,2,2-trifluoroacetic acid Chemical class OC(=O)C(F)(F)F.CCOC(=O)[C@@H]1CC[C@H](C)N1 VFRSADQPWYCXDG-LEUCUCNGSA-N 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 229940005657 pyrophosphoric acid Drugs 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000001235 sensitizing effect Effects 0.000 description 2
- 150000003460 sulfonic acids Chemical class 0.000 description 2
- ZZZQPNICTIZSQR-UHFFFAOYSA-N 3-ethoxy-n-phenylaniline Chemical compound CCOC1=CC=CC(NC=2C=CC=CC=2)=C1 ZZZQPNICTIZSQR-UHFFFAOYSA-N 0.000 description 1
- XFKRPUUIHKVIDM-UHFFFAOYSA-N 4,5-dinitronaphthalene-2,7-disulfonic acid Chemical compound [O-][N+](=O)C1=CC(S(O)(=O)=O)=CC2=CC(S(=O)(=O)O)=CC([N+]([O-])=O)=C21 XFKRPUUIHKVIDM-UHFFFAOYSA-N 0.000 description 1
- DJHGAFSJWGLOIV-UHFFFAOYSA-N Arsenic acid Chemical compound O[As](O)(O)=O DJHGAFSJWGLOIV-UHFFFAOYSA-N 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 244000166071 Shorea robusta Species 0.000 description 1
- 235000015076 Shorea robusta Nutrition 0.000 description 1
- DTQVDTLACAAQTR-UHFFFAOYSA-M Trifluoroacetate Chemical compound [O-]C(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-M 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229940000488 arsenic acid Drugs 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910001422 barium ion Inorganic materials 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- ZJHJWUVWYXNFLY-UHFFFAOYSA-N n-methoxy-n-phenylaniline Chemical compound C=1C=CC=CC=1N(OC)C1=CC=CC=C1 ZJHJWUVWYXNFLY-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- ATGUVEKSASEFFO-UHFFFAOYSA-N p-aminodiphenylamine Chemical compound C1=CC(N)=CC=C1NC1=CC=CC=C1 ATGUVEKSASEFFO-UHFFFAOYSA-N 0.000 description 1
- 238000004816 paper chromatography Methods 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/016—Diazonium salts or compounds
- G03F7/021—Macromolecular diazonium compounds; Macromolecular additives, e.g. binders
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/016—Diazonium salts or compounds
Definitions
- One object of the present invention is the production of a copying material for the photomechanical preparation of printing plates, especially flat and offset printing plates, the light sensitive layer of which comprises polyfunctional diphenylamine-4-diazonium salts, obtained by condensation of formaldehyde with diphenylamine-4-diazonium salts and which, although prepared by a technically simplified procedure, is in no way inferior and in many ways superior to the copying material mentioned above.
- the copying material according to the invention which consists of the carrier and the coating adhering thereon, which is made light sensitive by salts prepared by the condensation of diphenylamine-4-diazonium salts with formaldehyde in an acid selected from the group consisting of hydrofluoric acid, hydrochloric acid, hydrobromic acid, sulfuric acid and trifluoro acetic acid is characterized by the presence of metal salt-free polyfunctional diphenylamine-4-diazonium salts, of the above mentioned kind, as the light sensitive substance and excess phosphoric acid in the copying layer.
- phosphoric acid as used in the present case is meant to designate ortho phosphoric acid and the acids derived from ortho-phosphoric acid by splitting off water, such as pyrophosphoric acid, polyphosphoric acid and meta-phosphoric acid.
- pyrophosphoric acid such as pyrophosphoric acid, polyphosphoric acid and meta-phosphoric acid.
- polyphosphoric acid such as polyphosphoric acid
- meta-phosphoric acid such condensed phosphoric 3,236,646 Patented Feb. 22, 1966 acids are mentioned it is to be understood for definition in the present case, that 1 mole of such an acid is the amount which contains one mole of bound phosphorus.
- the ortho-phosphoric acid is preferred in the present case, since the salts of this acid are generally easily soluble in Water. I
- excess phosphoric acid is considered the amount of phosphoric acid per mole of diazonium groups, which exceeds 1.5 moles.
- 1.5 moles of phosphoric acid are also included primary phosphate ions of a diazonium phosphate.
- an acid phosphate of one of the above mentioned condensation products contains 0.5 mole excess phosphoric acid.
- the metal salt-free polyfunctional diazonium salts which may be used as the light sensitive substances for making the copying layer are for instance: nitrates, fiuoro borates, trifluoroaicetates, halides, phosphates or salts of sulfonic acids, which are applied to the carrier with or without the addition of a small amount of a film forming material, but in any case together with excess phosphoric acid.
- the phosphoric acid contained in the copying layer is of prime importance for the copying layer made according to the invention.
- copying material of the above described type in which the light sensitive substance in the copying layer consists of a metal salt-free neutral polyfunctional diazoniurn phosphate, obtained by condensation of diphenylamine-4-diazonium salt with formaldehyde in one of the acids mentioned above, and in which the copying layer contains either no additional or no more than 0.5 mole additional phosphoric acid per role of diazonium groups, aside from the primary phosphate ions derived from the neutral phosphate, also gives a printing material capable of producing a large amount of Well defined copies.
- An equivalent copying material is one in which the light sensitive substance in the copying layer consists of metal salt-free polyfunctional diazonium salts obtained by condensation of diphenylamine-4-diazonium salt with formaldehyde in an acid selected from the groups consisting of hydrofluoric acid, hydrochloric acid, hydro- 'bromic acid, sulfuric acid and trifiuoro acetic acid, and in which the copying layer contains from 0.05 to 1.5 moles of phosphoric acid per mole of diazonium groups.
- condensation products are used, which are prepared at room temperature or at a slightly elevated temperature, from unsubstituted or substituted diphenylamine-4-diazonium salts and formaldehyde in hydrofluoric acid, hydrochloric acid, hydrobromic acid, sulfuric acid or trifluoro acetic acid and are obtained as metal salt-free salts.
- substituted or unsubstituted diphenylamine-4-diazonium salts which are used as starting material for the production of the condensation products of the invention there are cited for example the diazotisation products at the following amino-compounds.
- the formaldehyde can be used as a concentrated aqueous solution. However, it is preferred to use gaseous formaldehyde or polymers of formaldehyde which are capable of spliting off formaldehyde under reaction conditions. Useful products, however, are also obtained if the molar ratio employed is smaller or larger than 1:1, but no larger than 2:1. To facilitate the isolation of the condensation products in solid form, the amount of the acid used as a condensation medium should be as small as possible.
- the salts of the condensation products are produced or precipitated according to different methods depending upon the condensation medium used.
- the condensation products can be isolated without decomposition by evaporating the condensation mixture to dryness at a temperature not exceeding 70 C., preferably under vacuum.
- Salts of condensation products are transformed to acid phosphates of the composition ArN H PO -H PO by dissolving them in strong phosphoric acid, blowing off the volatile acid, for instance hydrochloric acid, by means of a stream of dry gas and precipitating the desired product with organic solvents.
- the chlorides or bromides of the condensation products are prepared as follows: The condensation mixture is diluted with methanol, the calculated amount of chloride or bromide ions is added and, after removal of the sulfate ions, for example by treating with calcium carbonate, the mixture is evaporated to dryness.
- Ortho-phosphates, halides, fluorobora tes, and trifluoroacetates of the condensation products and the salts of sulfonic acids are products having good storageability, which are easily soluble in mixtures of water with waterrniscible solvents.
- the salts are also easily soluble in certain organic solvents, also in the presence of ortho-phosphoric acid and, therefore, can be combined with a number of additives soluble only in organic solvents.
- the ortho-phosphates of the condensation products are especially and more generally soluble in water. Salts of a low degree of condensation are usually easier to dissolve than those of a high degree of condensation.
- the salt of the condensation product is dissolved in water or mixtures of water with water-miscible solvents or mixtures of the solvents, then usually the phosphoric acid is added and the carrier material is coated in the usual manner, for example by wiping on or whirling on the solution.
- the use of solutions of the condensation products in organic solvents has the advantage of yielding more uniform coatings.
- the optimum concentration of the diazo compound in the coating solution is dependent upon the coating method, the coating conditions, and the carrier material. Usually, good copying layers are obtained if the concentration of diazonium salt in the coating solution is between 0.001 and 10% by weight. Higher concentrations are possible. However, no further advantage is usually obtained.
- the preferred range is between 0.02 and 5% by weight.
- the amount of the condensation product used depends somewhat on the base material used. For aluminum bases, the lower values in the preferred range are used e.g. between 0.05 and 0.5% by weight. It a paper base material is used generally more condensation product is used in the light sensitive coating e.g. from. 0.3 to 5 percent by weight.
- the optimum amount of phosphoric acid required for the stabilization of the coating also depends on the carrier material.
- phosphoric acid On brushed aluminum foils, coatings of good shelf life are obtained it 1.05 to 5 preferably 1.5 to 3 moles of phosphoric acid are used per mole of diazonium group. When neutral or acid phosphates of the condensation products are used, 0.05 to 4 or 0.01 to 3 moles of phosphoric acid per mole of diazonium group are added. If a paper carrier is used usually a larger amount of phosphoric acid is added e.g. from 2 to 30 preferably from 6 to 15 moles. In such a case part of the phosphoric acid may be replaced by another acid of low volatility e.g. sulfuric acid or arsenic acid. In this case the term excess phosphoric acid should also include such mixture of acids.
- additives commonly used in conjunction with diazo reproduction material such as oxidation inhibitors, film formers and others can be added.
- the preparation of the printing plates from the copying material of this invention is effected in the usual manner.
- the copying material is exposed under a negative and, after developing with, for example, water or aqueous solutions of gum arabic or emulsion lacquer developers, for example those described in US. Patent No. 2,754,279, a positive printing plate is obtained which accepts greasy ink very readily and is capable of long runs.
- Printing plates of even better quality are obtained if the use of aqueous developers prior to lacquering is omitted and the copying layer which has been exposed under a master is wiped instead with a water-miscible solvent, preferably ethylenegycol, polyglycol or glycerine, then the lacquer is applied and finally it is treated with aqueous compositions.
- a water-miscible solvent preferably ethylenegycol, polyglycol or glycerine
- parts by weight correspond to parts by volume as grams to millimeters.
- a brushed aluminum foil is coated with a solution containing 0.17 part by weight of a condensation product of 3-methoxy-diphenylamine-4-diazonium chloride and formaldehyde, condensed in 80% sulfuric acid and precipitated in the form of the chloride, and 0.13 part by weight of 85% phosphoric acid in a solvent mixture consisting of 8 parts by volume of water, 55 parts by volume of ethyleneglycol monomethylether and 37 parts by volume of dimethylformamide.
- the coated solution is dried at temperatures up to 100 C.
- the copying layer which has a good shelf life in the unexposed state, is exposed for to 60 seconds under a carbon arc, conventional in the trade, for example an 18 ampere lamp at a distance of about 60 cm.
- the exposed material is developed by wiping with water or an aqueous 14% gum arabic solution, which contains 0.06% of phosphoric acid.
- the printing master can be put on a printing machine immediately and is capable of reproducing a large number of perfect copies.
- the plate life can be considerably increased if a lacquer is applied, for instance a lacquer of the kind described in U.S. Patent No. 2,754,279.
- an electrolytically grained aluminum foil can be used instead of the brushed aluminum.
- the mixture is then poured into 200 parts by volume of saturated aqueous barium chloride solution, and further saturated barium chloride solution is added until no more barium or sulfate ions are detectable in the solution. Barium sulfate is separated, the solution is filtered over charcoal, and then evaporated to ryness under vacuum at a temperature not exceeding 60 C.
- Copying material of good quality is also obtained by using, instead of the salts mentioned above, equal quantities of the chloride or the bromide of a condensation product of 3-ethoxy-diphenylamine and formaldehyde prepared analogously.
- the chlorides and bromides of the condensation products made according to this method are obtained in the form of brown or brownish-green solids. They have good shelf life and are easy to ship (2)
- a brushed aluminum foil is coated with a solution consisting of 0.1 part by weight of a condensation product of diphenylamine-4-diazonium sulfate and formaldehyde, prepared in sulfuric acid and precipitated as the chloride, and 0.12 part by Weight of 85% phosphoric acid in admixture with 16 parts by volume of water, 110 parts by volume of ethyleneglycol monomethylether and 74 parts by volume of dimethyl-formamide.
- the bromide of the condensation product can be used for making the copying layer with similar results.
- the processing of the coating for making the printing plate is performed as described in Example 1.
- diphenylamine-4-diazonium sulfate 23 parts by weight of diphenylamine-4-diazonium sulfate are stirred into parts by volume of sulfuric acid (78%) during 1 hour, and then 2.4 parts by Weight of paraformaldehyde are added within 4 hours. The mixture is stirred for 2 hours at 40 C. and then left standing for 12 hours at room temperature.
- a brushed aluminum foil is coated with a solution of 0.14 part by weight of a condensation product of diphenylamine-4-diazonium chloride and formaldehyde prepared in hydrochloric acid and precipitated as the chloride, and 0.13 part by weight of 85% phosphoric acid in a mixture consisting of 8 parts by volume of water, parts by volume of ethyleneglycol monomethylether and 37 parts by volume of dimethylforamide.
- the printing form is made as described in Example 1.
- a copying layer of equal performance is obtained if, instead of 0.14 part by weight of the above mentioned condensation product, 0.16 part by weight of a condensation product of diphenylamine-4-diazonium chloride and formaldehyde, prepared in 66% hydrobromic acid and precipitated as the bromide, or 0.11 part by weight of a product made from diphenylamine-4-diazonium chloride and formaldehyde by condensation in 40% hydrofluoric acid, are dissolved and coated under identical conditions.
- the condensation products are prepared as follows:
- Condensation inv hydrobromic acid 138 parts by Weight of diphenylamine-4-diazonium chloride and 18 parts by Weight of paraformaldehyde are heated in 300 parts by volume of 66% hydrobromic acid for 7 hours to a temperature of 50 C. The mixture is then evaporated to dryness under vacuum at a maximum temperature of 70 C. The condensation product is obtained in the form of an acid bromide.
- Example 2 The preparation and use of the coating solution is as in Example 1, except that for preparing the solution, equimolecular amounts of trifiuoroacetate, fiuoroborate or 1,8-dinitronaphthalene-3,6-disulfonate of a condensation product are used which was prepared by condensing diphenylamine-4-diazonium salt and formaldehyde in sulfuric acid, under the conditions stated in Example 2.
- the printing plate is made as described in the examples above.
- Flu0r0b0rate The acid condensation mixtures are diluted with water and, upon addition of fluoboric acid, the fiuoroborate is precipitated. It is filtered off and dried.
- 1,8 dinitronaphthalene-3,6-disulf0nate.Raw condensation mixtures are diluted with water and mixed with aqueous solutions of the sulfonic acid or alkali salts of the sulfonic acid. The precipitate is separated off and dried.
- a brushed aluminum foil is coated with a solution containing 0.15 part by weight of a condensation product of diphenylamine-4-diazonium sulfate and formaldehyde, condensed in sulfuric acid and precipitated in the form of the acid phosphate, and 0.045 part by weight of 85% phosphoric acid in a mixture of 16 parts by volume of water, 110 parts by volume of ethyleneglycol monomethylether and 74 parts by volume of dimethyl formamide.
- the coated solution is dried at a temperature of about 100 C.
- the copying material has a good light sensitivity and shelf life and is converted into a printing plate as described in the foregoing examples.
- a condensation product obtained by condensation in a hydrohalide acid and precipitated as an acid phosphate can be used for making the copying layer.
- a chloride of a condensation product obtained by condensation of diphenylamine-4-diazonium salt with formaldehyde in sulfuric or hydrohalide acid.
- a dry stream of gas is passed through the mixture until chloride ions can no longer be detected.
- the mixture is then diluted with methanol and poured into isopropanol, whereupon the acid phosphate of the condensation product is precipitated, separated and dried.
- a base paper prepared in accordance with the teaching of US. patent specification No. 2,778,735 is coated with a solution containing, dissolved in 100 parts by volume of water, 3.7 parts by weight of 85 percent phosphoric acid and 1.31 parts by weight of a condensation product which was prepared by condensing 3-methoxy-diphenylamine-4-diazonium chloride and formaldehyde in sulfuric acid and obtained in the form of the chloride by adding chloride ions and removing the sulfuric acid.
- the diazonium salt required is prepared as described in Example 1.
- Example 1 After an exposure of 60 to 120 seconds under a negative master, using the carbon are lamp mentioned in Example 1 as a light source, and wiping over with water or dilute gum arabic solution, a positive printing plate is obtained from which long runs can be obtained.
- the reproduction material mentioned in the present example has a very good shelf life in the unexposed state.
- a reproduction material of good performance is also obtained when the base paper mentioned above is coated with a solution containing 1.6 parts by weight of the condensation product described below and 7 parts by weight of 85 percent phosphoric acid dissolved in 100 parts by volume of water.
- the condensation product is prepared as follows: 23.4 parts by weight of 4-methoxy-diphenylamine-4-diazonium sulfate are condensed with 1.67 parts by weight of paraformaldehyde in parts by volume of 78 percent sulfuric acid, first for one hour at C. and then for 12 hours at room temperature. As described above, the sulfate ions are precipitated by adding barium chloride to the solution, the barium sulfate is separated by filtration, and the filtrate is evaporated to dryness. 15 parts by weight are obtained of a mixture of the acid and the neutral chlorides of the condensation product.
- a brushed aluminum foil is coated with a solution containing 0.13 part by weight of a sulfate of a condensation product of a diphenylamine-4-diazonium salt and formaldehyde, prepared in sulfuric acid, and 0.11 part by weight of 85% phosphoric acid in 8 parts by volume of water, parts by volume of ethyleneglycol-monomethylether and 37 parts by volume of dimethylformamide.
- the sulfate of the high molecular weight condensation product, prepared in sulfuric acid can be obtained for example according to the teachings of U8. Patent 2,679,498.
- a superficially saponified cellulose acetate foil is coated with a solution containing 1 part by weight of a condensation product of diphenylamine-4-diazonium sulfate and formaldehyde, prepared in 96% sulfuric acid and precipitated in the form of the sulfate, following the method described in US. Patent No. 2,679,498, and 2 parts by weight of phosphoric acid in 100 ml. of water.
- the copying material which has a good shelf life, is developed by wiping with water, and is then inked up with greasy printing ink. A large number of flawless prints are obtained from this printing plate.
- a brushed aluminum foil is coated, on a plate whirler, with a solution containing 0.1 part by weight of a condensation product prepared from 4-methyl-diphenylamine-4'-diazonium sulfate and formaldehyde, by condensation in sulfuric acid and obtained in the form of the metal salt-free chloride, and 0.08 part by weight of 85 phosphoric acid, dissolved in a mixture of 8 parts by volume of water, 55 parts by volume of ethyleneglycol monomethylether, and 37 parts by volume of dimethylformamide.
- a condensation product prepared from 4-methyl-diphenylamine-4'-diazonium sulfate and formaldehyde, by condensation in sulfuric acid and obtained in the form of the metal salt-free chloride, and 0.08 part by weight of 85 phosphoric acid, dissolved in a mixture of 8 parts by volume of water, 55 parts by volume of ethyleneglycol monomethylether, and 37 parts by volume of dimethylformamide.
- the copying material thus obtained is converted into a printing plate from which long runs can be obtained.
- the condensation product mentioned above is prepared as follows:
- the acid phosphate of the condensation product is used, which is obtained from the chloride by dissolving the chloride in phosphoric acid removing the hydrochloric acid by passing a stream of gas, e.g. air, through the solution, and precipitating by means of organic solvents.
- a solution containing 0.14 part by weight of this condensation product, dissolved in a mixture consisting of 8 parts by volume of water, 54 parts by volume of ethyleneglycol monomethylether, and 37 parts by volume of dimethylformamide, may be used for coating.
- a reproduction material of equal performance is obtained if, instead of the chloride or the phosphate of the condensation product mentioned above equal amounts of the chlorides or phosphates of the condensation products prepared analogously from 3-methyl-diphenylaminel-diazonium salt or, respectively 3-methyl-diphenylamine-4'- diaz-onium salt, and formaldehyde are used for the prepa ration of the coating solution.
- Presensitized brushed aluminum foils of equal quality are obtained if, instead of the compounds mentioned above, a sensitizing solution is used containing 0.15 part by weight of the chloride of the condensation product of 4-methoxy-diphenylamine-4'-diazonium sulfate and formaldehyde described in Example 6 and 0.115 part by weight of 85 percent phosphoric acid in a mixture consisting of 8 parts by volume of water, 55 parts by volume of ethyleneglycol monomethylether, and 37 parts by volume of dimethylformamide.
- a paper base described in detail in US. Patent No. 2,778,735, is coated with a solution containing 2 parts by weight of a condensation product of diphenylamine-4- diazoniumphosphate-Z-carboxylic acid and formaldehyde, prepared in sulfuric acid and precipitated in the form of its bisulfate and 5 parts by weight of 85 percent phosphoric acid in 100 parts by volume of water.
- a copying material of good shelf life is thus obtained which, after exposure under a master and subsequent treatment with water, yields a printing plate from which a large number of flawless prints can be made.
- the bisulfate of the condensation product is prepared as follows:
- a copying material of equal quality is obtained if the paper base is sensitized with the bisulfate of a condensation product prepared, by the same method, from diphenylaminel-diazonium phosphate 2'-carboxylic acid.
- a brushed aluminum foil is coated in the usual manner with a solution containing 0.15 part by weight of a condensation product of diphenylamine-4-diazonium chloride and paraformaldehyde, prepared in concentrated hydrochloric acid and precipitated in the form of the acid chloride, and 0.5 part by volume of 0.1 molar phosphoric acid, dissolved in a mixture consisting of 55 parts by volume of ethyleneglycol monomethylether, 37 parts by volume of dimethylformamide, and 7.5 parts by volume of water.
- an aqueous gum arabic solution or treatment with an emulsion lacquer e.g. the one described in US. patent specification No. 2,754,279, a printing plate is obtained from which a large number of flawless prints can be obtained.
- a base paper manufactured in accordance with US. patent specification No. 2,778,735 is coated with a solution containing 2.3 parts by Weight of a condensation product prepared from 3-methoxy-diphenylamine-4-diazonium chloride and formaldehyde in hydrochloric acid and precipitated in the form of the chloride, 8 parts by weight of percent phosphoric acid and 2. parts by weight of concentrated sulfuric acid in parts by volume of Water. After exposure under a negative master and wiping over with water or a dilute aqueous solution of gum arabic, a positive printing plate is obtained from which long runs can be obtained. The reproduction ma terial prepared in this manner has a very good shelf life in the unexposed state.
- the diazonium chloride required is obtained as follows: 10.45 parts by weight of 3-methoxy-diphenylamine- 4-diazonium chloride are mixed with 1.21 parts by Weight of paraformaldehyde. The mixture is introduced into 20 parts by volume of concentrated hydrochloric acid and agitated, first for one hour at 40 C. and then for 20 hours at room temperature. Subsequently, the reaction mixture is evaporated to dryness under vacuum and at a temperature of 40 C. 11 parts by weight of a mixture are obtained consisting to about equal parts of the acid and the neutral chlorides of the condensation product.
- a reproduction material of equally good quality is obtained if, instead of the condensation product mentioned above, equivalent quantities of the chloride of a condensation product are used which is prepared analogously from 2-methoxy-diphenylamine-4-diazonium salt or 2- methoxy-diphenylamine-4-diazonium salt and formaldehyde.
- Example 11 The method described in Example 11 is followed, but for coating the brushed aluminum support a solution is used which contains 0.135 part by weight of the neutral polyfunctional diazonium phosphate described below and 0.008 part by weight of 85 percent phosphoric acid in a mixture consisting of 8 parts by volume of water, 55 parts by volume of ethyleneglycol monomethylether, and 37 parts by volume of dimethyl-formamide.
- diphenylamine-4-diazonium chloride is condensed with fomaldehyde in hydrochloric acid as described in Example 3.
- the chloride of the condensation product is then converted into the acid phosphate by the method described in Example 5.
- the acid phosphate is dissolved in water and the solution is treated with weakly basic ion exchanger, such as the one marketed by Merck, Darmstadt (Germany), under the designation Ionenor II, until a pH-value of 6 has been reached. Subsequently, the solvent is completely evaporated under vacuum at a temperature of 40 to 50 C.
- a presensitized printing plate comprising a base material having a coating thereon comprising at least one metal salt-free polyfunctional condensation product of a diphenylamine-4-diazonium salt with formaldehyde condensed in an acid selected from the group consisting of hydrofluoric acid, hydrochloric acid, hydrobromic acid, sulfuric acid, and trifiuoroacetic acid, and added excess phosphoric acid.
- a presensitized printing plate according to claim 1 in which the excess phosphoric acid is up to 30 moles of phosphoric acid per each mole of diazonium groups.
- a presensitized printing plate comprising a base material having a coating thereon comprising at least one neutral metal salt-free polyfunctional diazonium phosphate condensation product of a diphenylamine-4-diazonium salt with formaldehyde, containing, in addition to the phosphate ions of the neutral diazonium phosphate, no more than about 0.5 mole of added phosphoric acid per mole of diazonium groups.
- a presensitized printing plate comprising a base material having a coating thereon comprising at least one metal salt-free polyfunctional condensation product of a diphenylamine-4-diazonium salt with formaldehyde condensed in an acid selected from the group consisting of hydrofluoric acid, hydrochloric acid, hydrobromic acid, sulfuric acid, and trifiuoroacetic acid, and added phosphoric acid in an amount not exceeding about 1.5 moles per mole of diazonium groups.
- a presensitized printing plate in which the condensation product is employed in the form of a salt of the formula ArN X-nHX in which Ar is a condensed diphenylamine group, X is selected from the group consisting of fluorine, chlorine, and bromine, and n represents a number from O to 1.
- a presensitized printing plate according to claim 25 in which the paper base carries a coating containing from 2 to 30 moles of phosphoric acid per each mole of diazonium groups.
- a process for developing a printing plate which comprises exposing a supported layer to light under a master and treating the exposed layer with a developer, the layer comprising at least one metal saltree polyfunctional condensation product of a diphenylamine-4-diazonium salt with formaldehyde condensed in an acid selected from the group consisting of hydrofluoric acid, hydrochloric acid, hydrobromic acid, sulfuric acid, and trifiuoroacetic acid, and added excess phosphoric acid.
- a process for developing a printing plate which comprises exposing a supported layer to light under a master and treating the exposed layer with a developer, the layer comprising at least one neutral metal salt-free polyfunctional diazonium phosphate condensation product of a diphenylamine-4-diazonium salt with formaldehyde, containing, in addition to the phosphate ions of the neu tral diazonium phosphate, no more than about 0.5 mole of phosphoric acid per mole of added diazonium groups.
- a process for developing a printing plate which comprises exposing a supported layer to light under a master and treating the exposed layer with a developer, the layer comprising at least one metal salt-free polyfunctional condensation product of a diphenylamine-4-diazonium salt with formaldehyde condensed in an acid selected from the group consisting of hydrofluoric acid, hydrochloric acid, hydrobromic acid, sulfuric acid, and trifluoroacetic acid, and added phosphoric acid in an amount not exceeding about 1.5 moles per mole of diazonium groups.
- condensation product is employed in the form of a salt of the formula A1 N2H2PO4 H3PO4 in which Ar is a condensed diphenylamine group.
- condensation product is employed in the form of a salt of the formula ArN2X HX in which Ar is a condensed diphenylamine group, X is selected from the group consisting of fluorine, chlorine and bromine, and n is a number from O to 1.
- condensation pro-duct is employed in the form of a fluoroborate salt.
- condensation product is employed in the form of a salt of an organic sulfonic acid.
- condensation product is of a diphenylamine-4-diazonium phosphate with formaldehyde.
- condensation product is of a diphenylamine-4-diazonium chloride with formaldehyde.
- condensation product is of a diphenylamine-4-diazonium sulfate with formaldehyde.
- condensation product is of a 3-methoxy-diphenylamine-4-diazonium salt with formaldehyde.
- condensationfproduct is of a 4-methyl-diphenylamine-4-diazonium salt with formaldehyde.
- condensation product is of a 3-ethoxy-diphenylamine-4-diazonium salt with formaldehyde.
- condensation product is of a Z-methoxy-diphenylamine-4-diazonium salt with formaldehyde.
- condensation product is of a 3-methyl-diphenylamine-4-diazonium salt with formaldehyde.
- condensation product is of a 3-methyl-diphenylamine-4-diazonium salt with formaldehyde.
- condensation product is of 2-carboxy-diphenylamine-4-diazonium salt with formaldehyde.
- a presensitized printing plate comprising a base material having a coating thereon comprising at least one polyfunctional metal salt-free condensation product of a diphenylamine-4-diazonium salt with formaldehyde condensed in an acid selected from the group consisting of hydrofluoric acid, hydrochloric acid, hydrobromic acid, sulfuric acid, and trifluoroacetic acid, and at least 0.05 mole of added phosphoric acid per mole of diazonium groups.
- a process for developing a printing plate which comprises exposing a supported layer to light under a master and treating the exposed layer with a developer, the layer comprising at least one polyfunctional metal salt-free condensation product of a diphenylamine-4-diazonium salt with formaldehyde condensed in an acid selected from the group consisting of hydrofluoric acid, hydrochloric acid, hydrobromic acid, sulfuric acid, and trifluoroacetic acid, and at least 0.05 mole of added phosphoric acid per mole of diazonium groups.
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
- Printing Plates And Materials Therefor (AREA)
- Color Printing (AREA)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEK42721A DE1292001B (de) | 1961-01-25 | 1961-01-25 | Kopiermaterial fuer die photomechanische Herstellung von Flach- und Offsetdruckformen |
DEK0046364 | 1962-04-03 | ||
DEK0046365 | 1962-04-03 |
Publications (1)
Publication Number | Publication Date |
---|---|
US3236646A true US3236646A (en) | 1966-02-22 |
Family
ID=27211186
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US167910A Expired - Lifetime US3236646A (en) | 1961-01-25 | 1962-01-22 | Copying material for the photomechanical production of printing plates especially planographic and offset printing plates |
US269760A Expired - Lifetime US3235383A (en) | 1961-01-25 | 1963-04-01 | Reproduction material for the photomechanical preparation of planographic and offsetprinting plates |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US269760A Expired - Lifetime US3235383A (en) | 1961-01-25 | 1963-04-01 | Reproduction material for the photomechanical preparation of planographic and offsetprinting plates |
Country Status (9)
Country | Link |
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US (2) | US3236646A (es) |
BE (3) | BE630564A (es) |
CH (3) | CH434975A (es) |
DE (3) | DE1292001B (es) |
DK (2) | DK111658B (es) |
GB (3) | GB986683A (es) |
LU (3) | LU41133A1 (es) |
NL (5) | NL273557A (es) |
SE (3) | SE325778B (es) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3419394A (en) * | 1964-11-18 | 1968-12-31 | Dick Co Ab | Light sensitive lithographic plate of a water soluble diazo compound and a hydrophilic filler material |
DE2024242A1 (de) | 1969-05-20 | 1970-12-17 | Kalle Ag, 6202 Wiesbaden-Biebrich | Verfahren zur Herstellung lichtempfindlicher Verbindungen und mit diesen hergestelltes Kopiermaterial |
US3867147A (en) * | 1969-05-20 | 1975-02-18 | Hoechst Co American | Light-sensitive diazo compounds and reproduction material employing the same |
US4650739A (en) * | 1984-05-16 | 1987-03-17 | Hoechst Aktiengesellschaft | Process for post-treating aluminum oxide layers with aqueous solutions containing phosphoroxo anions in the manufacture of offset printing plates with radiation sensitive layer and printing plates therefor |
US5122442A (en) * | 1989-07-28 | 1992-06-16 | Hoechst Celanese Corporation | Method for forming an image from a high speed screen printing composition on a screen mesh |
EP0565006A2 (en) | 1992-04-06 | 1993-10-13 | Fuji Photo Film Co., Ltd. | Method for preparing PS plate |
EP0737894A2 (en) * | 1995-02-15 | 1996-10-16 | Agfa-Gevaert N.V. | A diazo based imaging element having improved storage stability |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3396020A (en) * | 1965-11-16 | 1968-08-06 | Azoplate Corp | Planographic printing plate |
NL168631C (nl) | 1969-05-20 | 1982-04-16 | Hoechst Ag | Registreermateriaal bestaande uit een drager waarop een laag is aangebracht die een lichtgevoelig condensatieprodukt van een diazoniumverbinding bevat. |
US4019907A (en) * | 1973-10-24 | 1977-04-26 | Hodogaya Chemical Co., Ltd. | Photosensitive azido color-forming element |
JPS5236697B2 (es) * | 1974-09-09 | 1977-09-17 | ||
US4299907A (en) * | 1978-08-10 | 1981-11-10 | Polychrome Corporation | Storage stable photosensitive diazo lithographic printing plates |
DE3135804A1 (de) * | 1981-09-10 | 1983-03-24 | Hoechst Ag, 6000 Frankfurt | Lichtempfindliches, diazoniumgruppen enthaltendes polykondensationsprodukt und damit hergestelltes lichtempfindliches aufzeichnungsmaterial |
Citations (6)
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US2266229A (en) * | 1941-12-16 | Ijnitfffc | ||
GB698040A (en) * | 1948-10-15 | 1953-10-07 | Kalle & Co Ag | Improvements relating to materials and processes for photo-lithographic printing |
US2679498A (en) * | 1954-05-25 | Atent office | ||
US2739889A (en) * | 1950-12-08 | 1956-03-27 | Azoplate Corp | Process for fixing lithographic diazotype printing foils having been exposed to light |
US2923703A (en) * | 1954-12-28 | 1960-02-02 | Kalvar Corp | Diazonium compounds |
US2937085A (en) * | 1954-01-11 | 1960-05-17 | Ditto Inc | Composite photosensitive plate, and method of making printing plate therefrom |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
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DE596731C (de) * | 1932-05-23 | 1934-05-09 | Kalle & Co Akt Ges | Verfahren zur Darstellung von hoehermolekularen Diazoverbindungen |
-
0
- BE BE630565D patent/BE630565A/xx unknown
- NL NL136718D patent/NL136718C/xx active
- BE BE613045D patent/BE613045A/xx unknown
- NL NL290568D patent/NL290568A/xx unknown
- NL NL290569D patent/NL290569A/xx unknown
- NL NL134368D patent/NL134368C/xx active
- BE BE630564D patent/BE630564A/xx unknown
- NL NL273557D patent/NL273557A/xx unknown
-
1961
- 1961-01-25 DE DEK42721A patent/DE1292001B/de not_active Withdrawn
-
1962
- 1962-01-16 GB GB1581/62A patent/GB986683A/en not_active Expired
- 1962-01-22 US US167910A patent/US3236646A/en not_active Expired - Lifetime
- 1962-01-23 LU LU41133D patent/LU41133A1/xx unknown
- 1962-01-24 SE SE00791/62A patent/SE325778B/xx unknown
- 1962-01-24 CH CH87862A patent/CH434975A/de unknown
- 1962-04-03 DE DE19621447001 patent/DE1447001A1/de active Pending
- 1962-04-03 DE DE1447002A patent/DE1447002C3/de not_active Expired
-
1963
- 1963-03-27 GB GB12181/63A patent/GB1028674A/en not_active Expired
- 1963-03-27 GB GB12182/63A patent/GB1017740A/en not_active Expired
- 1963-04-01 CH CH410063A patent/CH459759A/de unknown
- 1963-04-01 CH CH410163A patent/CH509612A/de not_active IP Right Cessation
- 1963-04-01 SE SE03575/63A patent/SE339407B/xx unknown
- 1963-04-01 SE SE03574/63A patent/SE339406B/xx unknown
- 1963-04-01 US US269760A patent/US3235383A/en not_active Expired - Lifetime
- 1963-04-02 DK DK151363AA patent/DK111658B/da unknown
- 1963-04-02 DK DK151263AA patent/DK111474B/da unknown
- 1963-04-03 LU LU43477D patent/LU43477A1/xx unknown
- 1963-04-03 LU LU43476D patent/LU43476A1/xx unknown
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
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US2266229A (en) * | 1941-12-16 | Ijnitfffc | ||
US2679498A (en) * | 1954-05-25 | Atent office | ||
GB698040A (en) * | 1948-10-15 | 1953-10-07 | Kalle & Co Ag | Improvements relating to materials and processes for photo-lithographic printing |
US2739889A (en) * | 1950-12-08 | 1956-03-27 | Azoplate Corp | Process for fixing lithographic diazotype printing foils having been exposed to light |
US2937085A (en) * | 1954-01-11 | 1960-05-17 | Ditto Inc | Composite photosensitive plate, and method of making printing plate therefrom |
US2923703A (en) * | 1954-12-28 | 1960-02-02 | Kalvar Corp | Diazonium compounds |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3419394A (en) * | 1964-11-18 | 1968-12-31 | Dick Co Ab | Light sensitive lithographic plate of a water soluble diazo compound and a hydrophilic filler material |
DE2024242A1 (de) | 1969-05-20 | 1970-12-17 | Kalle Ag, 6202 Wiesbaden-Biebrich | Verfahren zur Herstellung lichtempfindlicher Verbindungen und mit diesen hergestelltes Kopiermaterial |
US3867147A (en) * | 1969-05-20 | 1975-02-18 | Hoechst Co American | Light-sensitive diazo compounds and reproduction material employing the same |
DE2065733A1 (de) * | 1969-05-20 | 1975-09-04 | Hoechst Ag | Lichtempfindliches kopiermaterial |
US4650739A (en) * | 1984-05-16 | 1987-03-17 | Hoechst Aktiengesellschaft | Process for post-treating aluminum oxide layers with aqueous solutions containing phosphoroxo anions in the manufacture of offset printing plates with radiation sensitive layer and printing plates therefor |
US5122442A (en) * | 1989-07-28 | 1992-06-16 | Hoechst Celanese Corporation | Method for forming an image from a high speed screen printing composition on a screen mesh |
EP0565006A2 (en) | 1992-04-06 | 1993-10-13 | Fuji Photo Film Co., Ltd. | Method for preparing PS plate |
EP0737894A2 (en) * | 1995-02-15 | 1996-10-16 | Agfa-Gevaert N.V. | A diazo based imaging element having improved storage stability |
EP0737894A3 (en) * | 1995-02-15 | 1998-01-07 | Agfa-Gevaert N.V. | A diazo based imaging element having improved storage stability |
Also Published As
Publication number | Publication date |
---|---|
LU43476A1 (es) | 1963-07-29 |
SE325778B (es) | 1970-07-06 |
GB986683A (en) | 1965-03-24 |
NL134368C (es) | |
GB1028674A (en) | 1966-05-04 |
NL290568A (es) | |
DK111658B (da) | 1968-09-23 |
NL136718C (es) | |
DE1292001B (de) | 1969-04-03 |
DE1447002C3 (de) | 1974-01-17 |
BE613045A (es) | |
DE1447002A1 (de) | 1970-01-02 |
CH509612A (de) | 1971-06-30 |
CH459759A (de) | 1968-07-15 |
NL290569A (es) | |
BE630564A (es) | |
SE339407B (es) | 1971-10-04 |
LU43477A1 (es) | 1963-07-29 |
LU41133A1 (es) | 1962-03-23 |
CH434975A (de) | 1967-04-30 |
SE339406B (es) | 1971-10-04 |
DK111474B (da) | 1968-08-26 |
DE1447001A1 (de) | 1969-01-23 |
GB1017740A (en) | 1966-01-19 |
BE630565A (es) | |
NL273557A (es) | |
DE1447002B2 (de) | 1973-06-20 |
US3235383A (en) | 1966-02-15 |
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