US3397058A - Diazotype material - Google Patents

Diazotype material Download PDF

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Publication number
US3397058A
US3397058A US382670A US38267064A US3397058A US 3397058 A US3397058 A US 3397058A US 382670 A US382670 A US 382670A US 38267064 A US38267064 A US 38267064A US 3397058 A US3397058 A US 3397058A
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diazotype
diazo
light
azo
diazotype material
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Arie Van Loon
Ronc Hubertus Wilhelmus Maria
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Chemische Fabriek L Van Der Grinteen N V
Grinten Chem L V D
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Grinten Chem L V D
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    • 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

  • the invention relates to diazotype material of the socalled one-component type, which contains a p-amino benzene diazo compound, derived from a tertiary aromatic amine having only one aryl radical attached directly to the tertiary nitrogen atom, which compound in the para-position carries the diazo group and in one of the ortho-positions an etherified hydroxyl group.
  • the light-sensitive diazo compounds used in positive diazotype material are converted by irradiation with actinic light into compounds which are only slightly coloured, if at all, hereinafter called light-decomposition products.
  • the diazo compound left in the diazotype material after the imagewise exposure is converted into an azo-dyestutf during the so-called development following the imagewise exposure, by reaction with an azo-dyestuff component.
  • the light-decomposition products present in the exposed portions do not form an azo-dyestuif with the azo-dyestuff component.
  • the diazo compounds and azodyestutf components or mixtures of diazo compounds and/or mixtures of azo-dyestulf components preferably selected are those which form azo-dyestuffs producinggood contrasts, e.g. dark, such as blue or black, azo-dyestuffs.
  • Belgian Patent No. 564,343 describes a process in which diazotype material is used which contains a diazo compound of the type in which R represents an alkyl group with at most 4 carbon atoms and R represents an alkyl group with at most 4 carbon atoms or an aralkyl group with at most 7 carbon atoms, and in which R represents an alkyl group with at most 4 carbon atoms.
  • the diazo compounds of this type are very sensitive to the light of the mercury-vapour lamps that are frequently 3,397,058 Patented Aug. 13, 1968 employed in the diazotype process, both of the high-pressure lamps and of the low-pressure lamps, and both of the actinically fluorescent and of the non-fluorescent lamps.
  • Diazotype material sensitized with diazo compounds of this type is extremely suitable for the visual observation of the endpoint of the exposure in the process of copying in the light of actinically fluorescent mercury-vapour lamps.
  • diazotype material sensitized with diazo compounds of this type is quite different from the commonly used diazotype material sensitized with p-tert. aminobenzene diazo compounds having no alkoxy group ortho to the tert. amino group.
  • the latter diazotype material is much less lightsensitive and practically is not suited for the visual observation of the endpoint of the exposure.
  • the azo-dyestuffs of copies on diazotype material according to the said Belgian patent often show an undesirable change of colour in consequence of a decrease of pH occurring in the surface of the diazotype copies.
  • the said surface may turn acid or more acid, either 10- cally, e.g. by spilling of acid liquids, or all over, e.g. when the copies are kept in a humid atmosphere, owing to which the acid from the interior of the paper (as is known, basepaper for the diazotype process often contains comparatively large quantities of acid, e.g. in the form of alum) can diffuse to the surface.
  • diazo compounds are also very light-sensitive but when diazotype material is manufactured with these diazo compounds, the azo-dyestuffs of copies on such diazotype material are often found to show an undesirable change of colour owing to a decrease of the pH. Offshades in the incompletely exposed portions of the copies are also frequently obtained, especially when the chloro compounds are used.
  • Some of the above-mentioned very light-sensitive diazo compounds have such a low coupling activity that they are suited only for the manufacture of two-component diazotype material which is developed by exposure to ammonia vapour. Some of them have a greater coupling activity so that they are suited for the manufacture of one-component diazotype material which is developed by means of an alkaline-reacting developing liquid. None of those compounds, however, is suited for the manufacture of onecomponent diazotype material to be developed by means of an acid-reacting developing liquid. As is well known in the diazotype art, acid-reacting developing liquids are more stable than the alkaline-reacting developing liquids. So the impracticability of using the former involves a very important practical disadvantage.
  • the one-component diazotype material comprises a support sensitized with a light-sensitive composition containing, in the absence of an aZo-coupling component, a light-sensitive diazo compound of the formula in which /Rr N is selected from the class consisting of dialkylamino groups, N-ethyl N-benzylamino groups, N-alkyl-N-cyclohexylamino groups, (alkyl) (acyloxyalkyDamine groups, di(acyloxyalkyl)amino groups (in which groups the alkyl and benzyl radicals may carry further substituents) and the morpholino ring; R is a phenyl group, either substituted or unsubstituted; X is an anion and Y is selected from the class consisting of hydrogen and halogen atoms.
  • the aforesaid diazo compounds are new chemical compounds per se. Their light-decomposition products which are present, after the imagewise exposure, in the exposed image portions of copies on diazotype material accord ing to the present invention, form, during development, hardly any undesirable dyestuffs with diazo compound still present in those image portions.
  • the azo-dyestuffs of copies on diazotype material according to the present invention are highly resistant to a decrease of the pH.
  • the diazotype material according to the present invention additionally possesses the above-mentioned good properties possessed by the diazotype material used in the process of Belgian Patent No. 564,343.
  • the azo-dyestulf component 2,3-hydr0xynaphthoic acid-18- hydroxyethylamide if used in an alkaline-reacting developing liquid, causes more serious ofi-shades than does phloroglucinol in an alkaline-reacting developer.
  • Phloroglucinol in a developer with an acid reaction causes more serious off-shades than does phloroglucinol in an alkaline-reacting developer.
  • diazotype material according to the present invention When diazotype material according to the present invention is used, copies with hardly any off-shades are obtained in all these cases.
  • the diazo compounds and the dyestuff components of course have to be selected in such a way that their coupling activity is sufficient for the medium in which the formation of azo-dyestuff takes place.
  • Diazotype material according to the present invention which contains a diazo compound in which the amino group carries a benzyl group and an alkyl group is suitable for development with weakly acid, buffered phloroglucinol developers.
  • these developers in general have better resistance to oxidation than alkaline phloroglucinol developers. Copies on this material developed in such a way do not show off-shades owing to dyestufi formation by the light-decomposition products.
  • the diazo compounds which are used in the diazotype material according to the present invention also include compounds in which, besides the diazo group, the amino group and the phenoxy or substituted phenoxy group, the benzene nucleus carrying the diazo group carries yet another substituent, such as a halogen atom, in the paraposition with respect to the phenoxy or substituted phenoxy group.
  • Diazotype material according to the invention which contains a diazo compound in which the amino group carries a benzyl group and an alkyl group, and in which the benzene nucleus carrying the diazo group carries a chlorine atom in the para-position with respect to the phenoxy or substituted phenoxy group, is also very attractive. Owing to the great coupling activity .of the said diazo compound this diazotype material is especially suitable for development with weakly acid, buifered phloroglucinol developers, e.g. according to the so-called semi-wet process, in which a uniform thin layer of the developing liquid of, for example 8 g./m. is applied on the irnagewise exposed material. Copies on this material developed in such a way do not show off-shades owing to dyestufl formation by the light-decomposition products.
  • the phenoxy group may carry one or more substituents.
  • substituents are halogen atoms, alkoxy groups, methyl groups, monoand dialkylamino groups and others.
  • Diazotype material containing a diazo compound in which the phenoxy group carries at least one chlorine atom shows a greater speed of development than corresponding material containing the corresponding diazo compound with an unsubstituted phenoxy group.
  • the alkyl groups in the amino group may also carry substituents such as hydroxy, alkoxy, acyloxy, chloro, acylamino etc.
  • Diazotype material containing a diazo compound in which the amino group carries two acyloxyalkyl groups e.g. two acetyloxyethyl groups couples more actively upon development with a weakly acid buffered phloroglucinol developer than does corresponding diazotype material containing a diazo compound having the same structure but for the presence of two ethyl groups in the amino group.
  • acyloxy groups are: propionyloxy, butyryloxy, phenacetyloxy, chloroacetyloxy, benzoyloxy, furoyloxy, ethoxycarbonyloxy, phenylamidocarboxyloxy and methylsulphonyloxy groups.
  • diazo compounds may be especially mentioned as diazo compounds which may serve for the manufacture of diazotype material according to the present invention:
  • the diazotype material according to the invention may of course also contain mixtures of diazo compounds.
  • the nitroso or nitro compound or the azo-dyestuif thus obtained is reduced to an amino compound, and this amino compound is converted into a diazonium compound by treatment with nitrous acid.
  • the diazonium compound can be obtained as a double salt, e.g. by precipitation with zinc chloride, cadmium chloride, p-chlorobenzene sulphonic acid, sodium borofiuoride and the like.
  • starting material is p-chloro o-nitro chlorobenzene.
  • Example I White base-paper of Weight 80 g./m. as used for the diazotype process is sensitized with a solution of:
  • the sensitized surface contains approximately 0.45 millimole of diazo compound per m
  • the light-sensitive side of a sheet of the diazotype paper thus prepared is covered with a sheet of tracing paper, on which a pencil drawing has been made, and exposed in an exposure apparatus equipped with actinically fluorescent low-pressure mercury-vapour lamps. Exposure is continued until in the portions which are in contact with the blank parts of the drawings a small quantity or diazo compound is still left. The amount at which the exposure has to be terminated can be determined very well by visual observation (e.g. from the direction of the light-source) of the change of colour which occurs in the light-sensitive layer during the exposure. This moment is soon reached.
  • the latent diazotype copy thus obtained is developed by treating it with a developing liquid of the following composition:
  • the developed copy shows a violet-coloured image on uniformly foggy background which is also violetcoloured.
  • the violet azo-dyestuff is highly resistant to a decrease of the pH.
  • the diazo compound used according to this example is prepared as follows:
  • 2-aminodiphenylether is benzylated and then methylated.
  • the o-phenoxy N-benzyl N-methylaniline thus obtained (boiling point mm l94l97 C.) is nitrated, after which the p-nitro-o-phenoxy-N-benzyl-N-methylaniline is reduced and converted into the diazo compound in the usual way.
  • Example II White base-paper of Weight g./m. as used for the diazotype process is sensitized with a solution of:
  • the pH of the developing liquid is about 5.9.
  • the developed copy shOWS a black image on a uniformly foggy gray-coloured background.
  • the azo-dyestulf in the foggy background has the same colour as that in the black image portions.
  • the black azo-dyestulf is highly resistant to a decrease of the pH.
  • the diazo compound used according to this example is prepared as follows:
  • 2-p-chlorophenoxy-5-chloroaniline (commercially available under the name of Echtrot F.R. base) is benzylated.
  • the product thus obtained has a melting range between 78 and 80 C. It is methylated to 2-p-chlorophenoxy-S-chloro- N-methyl-N-benzyl-aniline, which is nitrated to 2-p-chlorophenoxy-4-nitro-5 chloro N methyl-N-benzylaniline (pale yellow crystals, melting point 102 C.). This compound is reduced and converted into the diazo compound in the usual way.
  • Example III 4 N methyl N-benzylamine S-p-chlorophenoxybenzene diazoniumchloride, zinc chloride double salt g 28 Citric acid g 5 Ethanol, 96% cm. 250 Water m 750 The excess of liquid is squeezed off and the sensitized layer is dried. It contains approximately 0.9 millimole of diazo compound per 111.
  • a sheet of the diazotype material thus prepared is imagewise exposed as described in Example I.
  • the endpoint of the exposure can be observed very well; it is reached very soon.
  • the latent diazotype copy thus obtained is developed by treating its image surface with a developing liquid of the following composition:
  • the developed copy shows a strong red image on a uniformly foggy background having the same red colour.
  • the red azo-dyestuff is highly resistant to a decrease of the pH. Upon. being wetted with a liquid with pH 2, it does not change its colour.
  • the diazo compound used according to this example is prepared as follows:
  • Example IV White base-paper of weight 80 g./m. as used for the diazotype process is sensitized with a solution of: 4-di(acetoxyethyl) amino-3-p-chlorophenoxy-6-chlorobenzene diazonium chloride zinc chloride double salt g 36 Tartaric acid g 5 1,3,6-naphthalene trisulphonic acid sodium salt g 30 Polyvinylacetate dispersion Vinnapas H.60 cm. 30 in 1000 cm. of water and dried.
  • the sensitized surface contains approximately 0.5 millimole of diazo compound per m.
  • the diazotype paper has good keeping qualities.
  • a sheet of the diazotype paper is image-wise exposed as described in Example I.
  • the endpoint of the exposure can be observed very well; it is reached very soon.
  • the latent diazotype copy thus obtained is developed by applying on its image-surface a layer of approximately 8 g./m. of a developing liquid of the following composition:
  • the sensitized surface contains approximately 0.46 millimole of diazo compound per m. about 92% is formed by the main component of the mixture of diazo compounds.
  • a sheet of the diazotype paper is image-wise exposed as described in Example I.
  • the endpoint of the exposure can be clearly observed; it is reached very soon.
  • the latent diazotype copy thus obtained is developed by applying on its image surface a layer of approximately 8 g./m. of a developing liquid of the following composition:
  • the pH of the developing liquid is about 6.3.
  • the developed copy shows a black image on a uniformly foggy background.
  • the image becomes visible considerably sooner than when, instead of the above-mentioned mixture of diazo compounds, exclusively 20.6 g. of the main component is used in the sensitizing liquid.
  • the azodyestutf in the foggy background has the same colour as that in the black image portions.
  • the black azo-dyestulf is highly resistant to a decrease of the pH.
  • the developed image may show some bleeding owing to the movement, during the development, of molecules of the diazo compound forming the main component of the mixture.
  • the azo-dyestufi portions show a non-sharp boundary in the form of an edge of clearly visible feathering varying in length between a few tenths of a millimetre and a few millimetres. This edge is completely absent, or much shorter, or much less visible, when the phenoxy group in the diazo compound forming the main component of the mixture carries a chlorine atom as substituent.
  • a one-component diazotype material comprising a support sensitized with a light-sensitive composition containing, in the absence of an azo coupling component, a light-sensitive diazo compound of the formula /R: XNg N in which is selected from the class consisting of dialkylamino groups, N-alkyl-N-benzylamino groups, N-alkyl-N-cyclohexylamino groups, (alkyl)(acyloxyalkyl)amino groups, di(acyloxyalkyl)amino groups and the morpholino ring,
  • R is a phenyl group
  • X is an anion
  • Y is selected from the class consisting of hydrogen and halogen atoms.
  • each of R and R is an alkyl group containing at most 2 carbon atoms, R is a chloro-phenyl group, and Y is a chlorine atom.
  • a one-component diazotype material comprising a support sensitized with a light-sensitive composition containing, in the absence of an azo coupling component, a light-sensitive l-diazo 4-dimethylamino 3-phenoxy benzene.
  • a one-component diazotype material comprising a support sensitized with a light-sensitive composition containing, in the absence of an azo coupling component, a light-sensitive l-diazo 4-(methyl) (benzyl) amino 3-phenoxy benzene.
  • a one-component diazotype material comprising a support, sensitized with a light-sensitive composition containing, in the absence of an azo coupling component, a
  • a one-component diazotype material comprising a support sensitized with a light-sensitive composition containing, in the absence of an azo coupling component, a light-sensitive l-diazo 4-dialkyl amino 3-p-chlorophenoxy 6-chlorobenzene in which the alkyl groups each contain at most 2 carbon atoms.
  • a one-component diazotype material comprising a support sensitized with a light-sensitive composition containing, in the absence of an azo coupling component, a light-sensitive l-diazo 4-dimethylamino 3-p-chlorophenoxy 6-chlor0benzene.
  • a process for the production of a diazotype print which comprises imagewise exposing to actinic light a diazotype material as defined in claim 1 and developing the exposed material by applying to it a film of a liquid developer containing phloroglucinol.

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  • 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)
US382670A 1958-11-10 1964-07-14 Diazotype material Expired - Lifetime US3397058A (en)

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DE (1) DE1174612B (en))
FR (1) FR1248122A (en))
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4267249A (en) * 1978-08-22 1981-05-12 Aerni-Leuch Ag Benzene diazonium salts and diazotype material utilizing same
US4411979A (en) * 1981-01-28 1983-10-25 Ricoh Company, Ltd. Diazo type thermosensitive recording material
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 (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL125383C (en)) * 1958-11-10
NL130247C (en)) * 1965-03-12
NL6711736A (en)) * 1966-08-26 1968-02-27
US3957489A (en) * 1968-09-11 1976-05-18 Gaf Corporation Solvent soluble diazonium metal salts and diazotype materials therefor
NL7009028A (en)) * 1970-06-19 1971-12-21
CA994329A (en) * 1972-03-24 1976-08-03 Ralph G.D. Moore Solvent soluble diazonium metal salts diazotype materials therefor

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE564343A (en)) * 1957-02-05
DE528606C (de) * 1928-03-03 1931-07-01 I G Farbenindustrie Akt Ges Verfahren zur Darstellung von Monoazofarbstoffen
GB425235A (en) * 1933-09-11 1935-03-11 Werner Paul Leuch Improvements in or relating to the production of photographic diazotype prints
US2405523A (en) * 1944-08-09 1946-08-06 Du Pont Light-sensitive photographic compositions and elements
DE865451C (de) * 1940-07-14 1953-02-02 Naphtol Chemie Offenbach Verfahren zur Herstellung von Diazoloesungen und leichtloeslicher Diazosalzpraeparate aus festen Diazoniumchlorid-Metallchlorid-Doppelsalzen
US3169869A (en) * 1958-06-04 1965-02-16 Grinten Chem L V D Diazotype material

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE528606C (de) * 1928-03-03 1931-07-01 I G Farbenindustrie Akt Ges Verfahren zur Darstellung von Monoazofarbstoffen
GB425235A (en) * 1933-09-11 1935-03-11 Werner Paul Leuch Improvements in or relating to the production of photographic diazotype prints
DE865451C (de) * 1940-07-14 1953-02-02 Naphtol Chemie Offenbach Verfahren zur Herstellung von Diazoloesungen und leichtloeslicher Diazosalzpraeparate aus festen Diazoniumchlorid-Metallchlorid-Doppelsalzen
US2405523A (en) * 1944-08-09 1946-08-06 Du Pont Light-sensitive photographic compositions and elements
BE564343A (en)) * 1957-02-05
US3169869A (en) * 1958-06-04 1965-02-16 Grinten Chem L V D Diazotype material

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4267249A (en) * 1978-08-22 1981-05-12 Aerni-Leuch Ag Benzene diazonium salts and diazotype material utilizing same
US4411979A (en) * 1981-01-28 1983-10-25 Ricoh Company, Ltd. Diazo type thermosensitive recording material
US4590263A (en) * 1982-09-30 1986-05-20 James River Graphics, Inc. High speed diazonium salts useful in diazo type photoreproduction

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DE1174612B (de) 1964-07-23
NL233064A (en))
CH386841A (de) 1965-01-15
FR1248122A (fr) 1960-10-31
NL98612C (en))
BE584387A (en))
GB919037A (en) 1963-02-20

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