US3442650A - Diazonium compounds and diazotype materials containing them - Google Patents

Diazonium compounds and diazotype materials containing them Download PDF

Info

Publication number
US3442650A
US3442650A US533257A US3442650DA US3442650A US 3442650 A US3442650 A US 3442650A US 533257 A US533257 A US 533257A US 3442650D A US3442650D A US 3442650DA US 3442650 A US3442650 A US 3442650A
Authority
US
United States
Prior art keywords
diazonium
diazotype
chlorophenoxy
compounds
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US533257A
Other languages
English (en)
Inventor
Andreas Joseph Johan Hendrickx
Bernardus Hubertus Huibers
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chemische Fabriek L Van der Grinten NV
Original Assignee
Grinten Chem L V D
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Grinten Chem L V D filed Critical Grinten Chem L V D
Application granted granted Critical
Publication of US3442650A publication Critical patent/US3442650A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • G03C1/54—Diazonium salts or diazo anhydrides

Definitions

  • Particularly suitable for one-component diazotype layers are 4-dialkylamino-3-(chloroor bromo-) phenoxy-Z-chlm robenzene diazonium compounds in which the alkyl groups contain at most four C atoms; materials made with these develop rapidly with weakly acid bufiered phloroglucinol solutions, yielding black images on bright white or foggy gray backgrounds.
  • the diazotype material may be so-called one-component diazotype material which is developed with a liquid containing an azo-coupling component, so-called two-component diazotype material which is developed with the aid of ammonia vapour, or heat-developable diazotype material.
  • diazonium compounds for sensitizing diazotype material should, as a rule, have a number of other properties. A very important one of these is that the photo-decomposition should form products which are completely or almost completely colourless, which when exposed to light show little or no staining and which do not actively react with diazonium compounds to yield dyestuffs.
  • diazonium compounds of very high light-sensitivity have come into use for sensitizing diazotype materials.
  • These compounds are chiefly benzene diazonium compounds having a tertiary amino group in the para-position with respect to the diazonium group and an etherified hydroxyl group in the meta-position, and possibly a further substituent, such as alkoxy, alkyl or halogen, in the para-position with respect to the etherified hydroxyl group.
  • benzene diazonium compounds having a tertiary amino group in the para-position with respect to the diazonium group and an etherified hydroxyl group in the meta-position, and possibly a further substituent, such as alkoxy, alkyl or halogen, in the para-position with respect to the etherified hydroxyl group.
  • diazonium compounds are also very light-sensitive; however, they have a higher coupling activity than the corresponding compounds with an alkoxy group in meta-position with respect to the diazonium group, and consequently are better suitable for application in onecomponent diazotype material which is developed with weakly acid buffered phloroglucinol developers.
  • One-component diazotype material sensitized with a diazonium compound according to general Formula I yields copies which present a somewhat stained completely exposed background and show a not-negligible yellowing when exposed for a considerable time to daylight or to the light of high-pressure mercury vapour lamps.
  • the invention relates to diazonium compounds of a new type and to diazotype material manufactured with the aid of these compounds, which material avoids or minimizes the disadvantages described above with respect to the known materials.
  • diazonium compounds of general Formula II in which X is an anion and Y is a halogen atom, R represents a substituted or non-substituted aryl group, R represents a substituted or non-substituted alkyl, branched alkyl or aralkyl group, and R represents a substituted or nonsubstituted alkyl, branched alkyl, cycloalkyl or aralkyl group.
  • the diazonium compounds according to the invention are very light-sensitive and yield both light-coloured and dark azo-dyestutfs with the azo-coupling components commonly used in the diazotype process. They couple more actively, bleach out more clearly, and form less reactive photo-decomposition products than the diazonium compounds according to general Formula I.
  • Diazotype materials sensitized with diazonium compounds according to the invention have a higher developing speed and yield copies which have a clearer completely exposed background and show less yellowing than corresponding diazotype material sensitized with a diazonium compound according to general Formula I.
  • the diazotype material according to the invention is preferably one-component diazotype material.
  • diazonium salts e.g. as diazonium chloride, sulfate, or metal chloride double salt, such as chlorozincate, chloromanganate and chlorostannate, as diazonium borofiuoride or diazonium aryl sulfonate.
  • diazotype materials can be applied in diazotype material individually, mixed together, or in admixture with diazonium compounds of other types. It goes without saying that a diazotype material according to the invention, accordingly as it contains a higher content of another diazonium compound, will present the specific advantages of the diazonium compounds according to the invention to a less degree.
  • the familiar supports such as paper, tracing paper, printing-plate paper, tracing linen, opaque linen, synthetic paper, metal sheets, glass fibre, polyester film and the like can be sensitized.
  • the diazonium compound may or may not be incorporated in a hydrophilic or hydrophobic film layer.
  • Preferred diazonium compounds according to the invention are those carrying a chlorine or a bromine atom in the ortho-position with respect to the diazonium group, a phenoxy group substituted with one or more halogen atoms in the meta-position, and in the para-position a dialkylamino group the substituted or non-substituted alkyl groups of which each carry at most 4 C-atoms.
  • diazotype material sensitized with these diazonium compounds furnishes copies in azo-dyestutfs which in the diazotype process are called neutral black.
  • the developing speed of such diazotype material is higher than that of diazotype materials sensitized with the corresponding diazonium compounds of general Formula I.
  • the completely exposed background of the copies is bright white; and shows-only little yellowing when exposed to daylight or to the light of a high-pressure mercury vapour lamp; the so-called foggy background of the copies is a fine neutral grey.
  • the conventional auxiliary agents can be used, e.g. acids, such as citric acid, tartaric acid and boric acid; stabilizers, such as benzene and naphthalene sulfonic acids, p-phenolsulfonic acid, and their water-soluble salts; metal salts, such as zinc chloride, magnesium chloride, nickel sulfate and alum; materials which serve to improve the developing speed, such as glycerol, polyethylene glycol, urea, thiosinamine and the like; surface-improving substances, such as finely divided silicon dioxide (colloidal or non-colloidal), aluminum oxide, barium sulfate and rice starch; binders, such as gelatin, gum arabic, cellulose ethers, starch derivatives, polyvinyl alcohol; dispersions of synthetic resins, such as dispersions of cationic, non-ionic, and anionic polyvinyl acetate; substances which serve to stabilize the background of
  • the phloroglucinol developers which are used in the one-component diazotype process often vary as to their composition and acidity. Below, two weakly acid phloroglucinol developers are described which are employed in practice and are used for development in a number of the following examples.
  • Developer A is a solution of:
  • Phloroglucinol g 4 Acetoacetanilide g 0.1 2-ethylhexyl sulfate ml 3 Beet sugar g 15 Benzoic acid g 2.5 Sodium benzoate g 14 Sodium formate g-- 135 in 1000 ml. of water.
  • the pH of this liquid is approximately 5.8.
  • Developer B is a solution of:
  • Phloroglucinol 6.5 Resorcinol 4 Thiourea 10 Sodium dibutylnaphthalene sulfonate 2 Sodium formate 14 Sodium benzoate 22 Trisodium citrate (2 aq.) 49 Citric acid 1.2
  • the pH of this liquid is approximately 6.5.
  • EXAMPLE I A sheet of white base paper for the diazotype process, of weight g./m. is sensitized with a liquid containing:
  • diazoty-pe papers are very light-sensitive.
  • Diazotype paper A develops somewhat more rapidly than diazotype paper B.
  • a strip of each sheet is imagewise exposed underneath a transparent ink drawing until the diazonium compound underneath the image-free portions of the drawing has completely bleached out, and then both are developed with developer B.
  • the copies thus obtained show a black image on a white background.
  • the background of copy A is whiter than that of copy B, and moreover it shows less yellowing when the copies are exposed to daylight or to the light of a high-pressure mercury vapour lamp.
  • the diazonium compound according to the invention used in this example was prepared as follows:
  • EXAMPLE II White base paper for the diazotype process, of weight 80 g./m. is sensitized with a solution containing 4-di('-acetoxyethyl amino-3-(4'-chlorophenoxy)-2- chlorobenzene diazonium chloride, zinc chloride in 1000 ml. of water and dried.
  • a sheet of the diazotype paper thus obtained is imagewise exposed underneath a transparent ink drawing until the diazonium compound underneath the image-free portions of the drawing has completely bleached out, and is then developed with developer A.
  • the copy shows a violet-black image on a bright white background.
  • the diazotype paper thus obtained develops somewhat more slowly, bleaches out with a somewhat more pronounced stain, and gives copies which show stronger yellowing when exposed to daylight.
  • the diazonium compound used in this example was prepared as follows:
  • the nitro group of 3-chloro-2-(4-chlorophenoxy) nitrobenzene was reduced to an amino group, which was converted with epoxyethane into a di-(2-hydroxyethyl) amino group, from which a di(2'-acetoxyethyl)amino group was obtained with the aid of acetic anhydride.
  • the product thus prepared was nitrated.
  • the diazonium salt was prepared in the usual way by reduction and diazotization.
  • the plate After the development, the plate is sponged off with water. It shows a white image on a yellow background.
  • the plate is placed in an olfset printer. At least 100 good positive offsetprints can be made from it.
  • the diazonium compound used in this example was prepared as follows:
  • 3-chloro-2-(4'-chlorophenoxy)aniline was tosylated, nitrated, and methylated. After saponification of the tosylamino group the 4 nitro-3-chloro-2-(4'-chlorophenoxy)- N-methylaniline obtained was benzylated. From the 4- nitro-3-chloro 2 (4' chlorophenoxy) N methyl N- benzylaniline, the diazonium salt was obtained in the usual way by reduction and diazotization.
  • X is an anion
  • Y is a halogen atom
  • R is a non-substituted or lower alkylor halogensubstituted phenyl group
  • R is a lower alkyl, lower branched alkyl or benzyl group
  • R is a lower alkyl, lower branched alkyl, cyclohexyl or benzyl group.
  • R is a halogen-substituted phenyl group and each of R and R is an alkyl group having at most 4 C atoms.
  • a diazonium compound according to claim 1 namely, a 4 dialkylamino 3 chlorophenoxy-Z-chlorobenzene diazonium compound.
  • a diazonium compound according to claim 1 namely, a 4 N alkyl-N-benzylamino 3 chlorophenoxy- 2-chlorobenzene diazonium compound.
  • a diazonium compound according to claim 1 namely, a 4 N benzyl-N-cyclohexylamino 3 cyclophenoxy- 2-chl0robenzene diazonium compound.
  • a diazonium compound according to claim 1 namely, a 4 dimethylamino 3 chlorophenoxy-Z-chlorobenzene diazonium compound.
  • a diazonium compound according to claim 1 namely, a 4 N methyl-N-benzylamino-3-chlorophenoxy- 2-chlorobenzene diazonium compound.
  • a diazotype material comprising a support carrying a light-sensitive layer containing a diazonium compound as defined in claim 1.
  • a one-component diazotype material comprising a support carrying a light-sensitive layer containing, in the 7 8 substantial absence of an azo coupling component, a NORMAN G. TORCHIN, Primary Examiner. diazonium compound as defined in claim 2.
  • Q BOWERS Assistant Examiner References Cited Us CL X FOREIGN PATENTS 5 260-141, 142; 96-49, 75, 33

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US533257A 1965-03-12 1966-03-10 Diazonium compounds and diazotype materials containing them Expired - Lifetime US3442650A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
NL6503184A NL6503184A (enrdf_load_stackoverflow) 1965-03-12 1965-03-12

Publications (1)

Publication Number Publication Date
US3442650A true US3442650A (en) 1969-05-06

Family

ID=19792646

Family Applications (1)

Application Number Title Priority Date Filing Date
US533257A Expired - Lifetime US3442650A (en) 1965-03-12 1966-03-10 Diazonium compounds and diazotype materials containing them

Country Status (5)

Country Link
US (1) US3442650A (enrdf_load_stackoverflow)
DE (1) DE1693191B2 (enrdf_load_stackoverflow)
GB (1) GB1081274A (enrdf_load_stackoverflow)
NL (2) NL6503184A (enrdf_load_stackoverflow)
SE (1) SE334163B (enrdf_load_stackoverflow)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3634090A (en) * 1968-09-03 1972-01-11 Keuffel & Esser Co Light sensitive one-component diazotype material
US3775131A (en) * 1970-06-19 1973-11-27 Oce Van Der Grinten Nv Diazonium compounds and diazotype materials containing them
US3944423A (en) * 1968-09-03 1976-03-16 Keuffel & Esser Company Light-sensitive diazotype material comprising a fluoroalkoxy-substituted diazonium compound
US4590263A (en) * 1982-09-30 1986-05-20 James River Graphics, Inc. High speed diazonium salts useful in diazo type photoreproduction

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4312708A1 (de) * 1993-04-20 1994-10-27 Hoechst Ag Verfahren zur Herstellung von aromatischen Aminen und Diazoniumsalzen

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB919037A (en) * 1958-11-10 1963-02-20 Grinten Chem L V D Diazotype material
NL6407303A (enrdf_load_stackoverflow) * 1963-07-06 1965-01-07

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB919037A (en) * 1958-11-10 1963-02-20 Grinten Chem L V D Diazotype material
NL6407303A (enrdf_load_stackoverflow) * 1963-07-06 1965-01-07

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3634090A (en) * 1968-09-03 1972-01-11 Keuffel & Esser Co Light sensitive one-component diazotype material
US3944423A (en) * 1968-09-03 1976-03-16 Keuffel & Esser Company Light-sensitive diazotype material comprising a fluoroalkoxy-substituted diazonium compound
US3775131A (en) * 1970-06-19 1973-11-27 Oce Van Der Grinten Nv Diazonium compounds and diazotype materials containing them
US4590263A (en) * 1982-09-30 1986-05-20 James River Graphics, Inc. High speed diazonium salts useful in diazo type photoreproduction

Also Published As

Publication number Publication date
SE334163B (enrdf_load_stackoverflow) 1971-04-19
NL6503184A (enrdf_load_stackoverflow) 1966-09-13
DE1693191B2 (de) 1980-07-03
GB1081274A (en) 1967-08-31
NL130247C (enrdf_load_stackoverflow)
DE1693191A1 (de) 1971-06-24

Similar Documents

Publication Publication Date Title
US2245628A (en) Reflex copying process
US3248220A (en) Two-component diazotype material
US3520692A (en) Diazonium compounds and diazotype materials containing them
US3442650A (en) Diazonium compounds and diazotype materials containing them
US3311475A (en) Diazotype material
US3338713A (en) Diazotype material
US3442652A (en) Diazonium compounds and diazotype material
US3169869A (en) Diazotype material
US3397058A (en) Diazotype material
US2552354A (en) Diazotype layers containing diazos of n-(2-hydroxypropyl)-phenylenediamines
US3622325A (en) Diazotype photographic copying material adapted for wet development and for producing copied image in black color
US3442651A (en) Diazonium compounds and diazotype materials containing them
US3397985A (en) Light sensitive diazotype material and diazonium compounds therefor
US3416924A (en) Heat-developable diazotype material
US2560137A (en) Diazotype photoprinting material
US3573051A (en) Two-component diazotype composition
US3775131A (en) Diazonium compounds and diazotype materials containing them
US3769018A (en) Diazotype materials containing resorcinol mono(aryloxy or arylthio)alkyl ethers
US3560215A (en) Light-sensitive diazotype material
US3459550A (en) Diazotype material
US2688543A (en) Poly-acetoacetyl derivatives of polyamines as azo components in diazotype photoprinting material
US3238044A (en) One-component diazotype material
US3607275A (en) Diazo-type material
US3944423A (en) Light-sensitive diazotype material comprising a fluoroalkoxy-substituted diazonium compound
US3761263A (en) Diazotype compositions and photographic processes