US3397985A - Light sensitive diazotype material and diazonium compounds therefor - Google Patents

Light sensitive diazotype material and diazonium compounds therefor Download PDF

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US3397985A
US3397985A US422693A US42269364A US3397985A US 3397985 A US3397985 A US 3397985A US 422693 A US422693 A US 422693A US 42269364 A US42269364 A US 42269364A US 3397985 A US3397985 A US 3397985A
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diazo
pyrrolidon
diazotype
paper
group
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Hendrickx Andreas Jos Johannes
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Van der Grinten NV
Canon Production Printing Holding BV
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Oce Van der Grinten NV
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/18—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
    • C07D207/22—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D207/24—Oxygen or sulfur atoms
    • C07D207/26—2-Pyrrolidones
    • C07D207/263—2-Pyrrolidones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms
    • C07D207/27—2-Pyrrolidones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms with substituted hydrocarbon radicals directly attached to the ring nitrogen atom
    • 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 containing a benzene diazonium salt of a new type and more particularly to one-component diazotype material which is very suitable for development according to the so-called thin layer method with weakly acid 'buifered developing liquids commonly used in the one-component diazotype process.
  • Diazotype materials can be distinguished into: onecomponent diazotype materials, which are developed with the aid of a liquid containing an azo-cou'pling component', two-component diazotype materials, which are developed with the aid of gaseous alkali (ammonia); heat-developable diazotype materials; planographic printing plates sensitized with diazo compounds.
  • One-component diazotype material is usually developed by spreading (after imagewise exposure) a thin layer (4-12 g./m. of an aqueous developing liquid on the sensitized surface (and also on the non-sensitized surface, if desired).
  • the developing liquids commonly used in the one-component diazotype process are usually distinguished into alkaline liquids having a pH above 7 and buffered weakly acid liquids the pH of which is between 5.5 and 7. Because of their high keeping quality the weakly acid developers are to be preferred to the alkaline developers.
  • phloroglucinol which in alkaline medium is readily oxidized by the oxygen from the air, is practically always used as azo-coupling component.
  • Developers, both alkaline and buifered Weakly acid developers, which contain phloroglucinol as 2120- coupling component, often in combination with a quantity of resorcinol, are used on a large scale in practice.
  • diazotype materials which can be developed with a weakly acid bulfered developer
  • various diazo compounds derived from hydroquinone dialkyl and diaralkyl ethers and having high coupling activity are employed.
  • Groups of such diazo compounds are: those with the general atent O 3,397,985 Patented Aug.
  • R and R are alkyl or aralkyl groups
  • R stands for a substituted or a non-substituted alkyl, aralkyl, aryl, alkoxy, aralkoxy, aryloxy, a substituted amidocarbonyl or a substituted amido radical
  • R for a hydrogen atom or an alkyl group or is an alkyl or acyl group which forms a heterocyclic ring with N-COR (See: British patent specifications Nos.
  • the diazo compounds according to the formulae of FIGURES 14 upon exposure yield a somewhat stained photo-decomposition product, so that copies made on a diazotype material sensitized with such a compound show a stained background.
  • the support of the diazotype material is white paper, the background of the copies instead of being bright white, shows a somewhat dingy stain; when the support is transparent, the copieseven if the azo-dyestuif image has high absorption for ultraviolet radiation-are not very suitable as intermediate originals for making further copies on diazotype material, because the presence of the stained photo-decomposition product in the image-free portions of the intermediate original decreases its transparency to the ultra-violet copying radiation, and thus necessitates a longer exposure time when further copies are to be made.
  • diazotype materials according to the Dutch patent applications Nos. 288,469 and 295,561 have a higher developing speed than diazotype material which has been sensitized with a similar diazo compound, derived from hydroquinone, according to the formulae of FIGURES 1-4, and they are often more light-sensitive as Well, particularly when R is a small alkyl group.
  • the present invention relates to diazotype material characterized in that it contains a diazo compound of the-general 'formula according to FIGURE 7, in which X is an anion, R stands for an alkyl (Le, a non-branched ir branched alkyl), alkenyl, cycloalkyl, aralkyl, or aryl group, and Y for a substituent from the group formed by acylamino, etherified mercapto, dihydrotriazinyl, and substituted or non-substituted phenyl groups.
  • X is an anion
  • R stands for an alkyl (Le, a non-branched ir branched alkyl), alkenyl, cycloalkyl, aralkyl, or aryl group
  • Y for a substituent from the group formed by acylamino, etherified mercapto, dihydrotriazinyl, and substituted or non-substituted
  • acylamino is to be understood that radical in which R; stands for an organic radical and R for a hydrogen atom, an alkyl or aralkyl group, or for an alkyl or acyl radical which forms a heterocyclic ring with NCOR
  • R stands for an organic radical and R for a hydrogen atom, an alkyl or aralkyl group, or for an alkyl or acyl radical which forms a heterocyclic ring with NCOR
  • the diazotype material according to the invention is a little more light-sensitive and as a rule has better keeping quality. Besides, it bleaches out brighter.
  • diazotype material according to the invention bleaches out bright is manifest when the material, while being printed, has a high moisture content, for instance because it has been kept in a humid atmosphere for some hours.
  • copies made of diazotype paper according to the invention which has been left unpacked, e.g. for an hour in an ofiice room having a temperature of 20 C. and a relatively humidity of 75% before the copies were made, show a much whiter background than copies on diazotype materials sensitized with diazo compounds according to the formulae of FIGURES 1-6 and stored under the same conditions.
  • the diazotype material according to the invention is preferably one-component diazotype material. Upon development with weaky acid phloroglucinol developers it yields properly developed copies with strong red to very dark-brown azo-dyestufi images. (Of course, one-component diazotype material according to the invention can be developed with weakly alkaline developing liquids; copies also showing strong, somewhat lighter, red to brown azodyestufis are then obtained). The diazotype material according to the invention may also be heatdevelopable diazotype material.
  • Diazo compounds which can be used in the diazotype material according to the invention are:
  • the diazo compounds are used as diazonium salts, for instance as chlorides or sulfates, or as diazonium metal double salts, such as the zinc chloride double salt, the manganese chloride double salt, and the stannic chloride double salt, or as borofluorides. They can be applied separately, mixed together, or in admixture with diazo compounds of other types. It is obvious that, when mixtures are used, the effect of the new diazo compounds will be smaller according as a larger quantity of the other compound(s) is used.
  • the diazo compounds according to the invention have high coupling activity and good light-sensitivity, moreover bleach out while forming practically colourless photo-decomposition products, and yield highcontrast azo-dyestuffs with the conventional azocoupling components, such as phloroglucinol and resorcinol, nevertheless there are differences in qualities and accessibility between the various diazo compounds.
  • diazo compounds having a benzoylamino or an etherified mercapto group in para-position relative to the diazo group are preferred.
  • Diazotype materials which have good keeping quality, develop very rapidly, and are reasonably inexpensive can be prepared with these diazo compounds.
  • Very useful compounds are, for instance, those of the general formula according to FIGURE 8 in Which R represents a non-branched alkyl group having up to 5 carbon atoms and X represents an anion.
  • Particularly valuable diazo compounds are those with an alkyl, aralkyl, or arylthio group in para-position and more especially those of the general formula according to FIGURE 9, in which R represents a non-branched alkyl group having up to 5 carbon atoms, R represents a non-branched alkyl group having up to 4 carbon atoms or a substituted or non-substituted benzyl or phenyl group, and X represents an anion.
  • Diazotype material sensitized therewith has. higher light-sensitivity than diazotype material according to the invention containing a diazo compound with another substituent in para-position.
  • the support to be used may be paper, printing-plate paper, tracing paper, transparentized paper, linen, tracing linen, synthetic paper, film material, such as films of cellulose acetate and polyester, metal, e.g. planographic printing plates of aluminium.
  • diazotype material according to the invention may contain the additions commonly used in the diazotype process, e.g. acids, such as citric acid, tartaric acid, and boric acid; stabilizers, such as benzene and naphthalene sulfonic acids and their water-soluble salts, e.g.
  • acids such as citric acid, tartaric acid, and boric acid
  • stabilizers such as benzene and naphthalene sulfonic acids and their water-soluble salts, e.g.
  • sodium napthalene 1,3,6-trisulfonate metal salts, such as zinc chloride, magnesium chloride, nickel sulfate, and alum; surface-improving substances, such as finely divided silica (colloidal or non-colloidal), aluminium oxide, barium sulfate, rice starch, etc.; binders, such as gelatin, gum arabic, cellulose ethers, starch derivatives, polyvinyl alcohol; dispersions of synthetic resins, such as dispersions of polyvinyl acetate in aqueous media containing cationic, non-ionic or anionic dispersing agents.
  • metal salts such as zinc chloride, magnesium chloride, nickel sulfate, and alum
  • surface-improving substances such as finely divided silica (colloidal or non-colloidal), aluminium oxide, barium sulfate, rice starch, etc.
  • binders such as gelatin, gum arabic, cellulose ethers, starch derivatives
  • the phloroglucinol developers which are used in the one-component diazotype process often vary as to their composition and acidity. Below three weakly acid phloroglucinol developers employed in practice are described. These developers will be used for development in the following examples.
  • Developer A is a solution of:
  • Phloroglucinol g .4 Acetoacetanilide 0.1 2-ethyl-1-hexanol sulfate Tergitol 08 (from Union Carbide & Carbon Corp., New York 17, U.S.A.;
  • Tergitol is a registered trademark) 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 butylnaphthalene sulfonate Sorbit P (from Geigy Chem. Corp. Ardsley, N.Y., U.S.A.; the
  • the pH of this liquid is 6.5.
  • Developer C is a solution of:
  • the weakly acid buffered developers may also contain other azo-coupling components having high coupling activity, e.g. 2,3 dihydroxynaphthalene, and acetoacetanilide.
  • azo-coupling components having high coupling activity e.g. 2,3 dihydroxynaphthalene, and acetoacetanilide.
  • Example I Three sensitizing liquids are prepared: (A) A liquid containing:
  • (B) A similar liquid to that mentioned under (A), but containing, instead of the 4-benzoylamino-2-pyrrolidon- (2)yl(1)-5- methoxybenzene diazonium salt, and equimolar quantity of 4-benzoylamino-2-N-methyl-N-acetylamino-Sanethoxy benzene diazonium chloride, zinc chloride double salt.
  • a sheet of white base paper of weight g./m. and suitable for the diazotype process is sensitized. After sensitization the three sheets are dried. Each sheet contains approximately 0.40 millimol of diazo compound per m A strip of each sheet is imagewise exposed underneath a transparent ink drawing for the time required to bleach out, on the strip of sheet (A), all the diazo compound underneath the image-free portions of the original. After this, the strips are developed with developer (A).
  • Strip (A) shows a violet-brown image on a bright white background.
  • Strip (B) shows a dark brown image on a somewhat foggy background, and strip (C) shows a black image on a heavy violet-grey background.
  • a second strip of the sheets (A), (B) and (C), screened from the light, is kept for an hour in a room having a relative humidity of 75% and a temperature of approximately 20 C.
  • the strips are then fed, together with a transparent ink rdrawing, through a continuously operating exposure apparatus for the diazotype process comprising an exposure cylinder of glass which has a surface temperature of approximately 60 C. and in which a high-pressure mercury vapour lamp is mounted, with such a speed that, on strip (C), all the diazo compound underneath the image-free portions of the drawing has bleached out.
  • the strips are then developed with developer (A). It is clearly visible that the white background of the strips (B) and (C) is less white than that of strip (A).
  • the 2-pyrrolidon(2)yl(1) diazo compound used in the example was prepared as follows: p-aminophenol was brought into reaction with -butyrolactone. Thus 4-pyrrolidon(2)yl(1)phenol was formed, which product was nitrated and then methylated with dimethyl sulfate. The nitro group was reduced to an amino group and the amino group was benzoylated.
  • the 4-pyrrolidon(2)yl(l)-2- benzoylaminoanisole was nitrated to 4-pyrrolidon(2)yl- (1)-2-benzoylamino-S-nitroanisole, which melts at 223- 225 C. Upon reduction, 4-benzoylamino-Z-pyrrolidon- (2)yl(l)-5-methoxyaniline was formed, which product was diazotizecl. The diazo compound was obtained in the form of the chlorozincate.
  • EXAMPLE II White base paper of weight 80 g./m. and suitable for the diazotype process is sensitized with a liquid containing:
  • the diazotype paper thus obtained contains approxi n1ately 0.45 millimol of diazo compound per m2.
  • a sheet of the diazotype paper is imagewise exposed underneath a transparent ink drawing until all the diazo compound underneath the image-free portions of the drawing has bleached out, and is then developed with developer (A).
  • the copy shows a red image on a bright White background.
  • the diazotype paper thus obtained is considerably less light-sensitive, and gives copies with a black azo-dye-stuff image on a background having a somewhat dingy stain.
  • the diazo compound used in the example was prepared as follows: 2-hydroxybiphenyl was methylated and then nitrated. The nitro group of the 2-methoxy-5-nitrobiphenyl was reduced and the amino group thus obtained was brought into reaction with -butyrolactone. The 2-phenyl- 4-pyrrolidon(2)yl(l)anis0le thus prepared was nitrated to 4 phenyl-2-pyrrolidon(2)yl(l)-5-methoxynitrobenzene, which melts at 123 C. From this nitro compound the di azo compound was prepared by reduction and diazotization; it was obtained in the form of the chlorozincate.
  • a sheet of white base paper of weight g./m. and suitable for the diazotype process is sensitized. After sensitization the three sheets are dried. Each sheet contains approximately 0.37 millimol of diazo compound per m.
  • a strip of each sheet is imagewise exposed underneath a transparent ink drawing for the time required to bleach out on the strip of sheet (A), all the diazo compound onderneath the image-free portions of the original. After this, the strips are developed with developer (B).
  • Strip (A) shows a brown image on a bright white background.
  • Strip (B) shows a dark brown image on a somewhat foggy light brown background.
  • Strip (C) shows a green-black image on a heavily foggy grey background.
  • a second strip of the sheets (A), (B), and (C), screened from the light, is stored for an hour in a room with a relative humidity of 75% and a temperature of approximately 20 C.
  • the strips are then fed, together with a transparent ink drawing, through a continuously operating exposure apparatus for the diazotype process with an exposure cylinder of glass which has a surface temperature of approximately 60 C. and in which a high-pressure meroury vapour lamp is mounted, with such a speed that on strip (C) all the diazo compound underneath the imagefree portions of the drawing has bleached out.
  • the strips are then developed with developer (B).
  • the white background of the strips (B) and (C) is far less white than that of strip (A).
  • the diazo compound with the 2-pyrrolidon(2)yl(l) group used in the example was prepared as follows: 4-pyrrolidon(2)yl(l) 2 nitroanisole was reduced to 5-pyrrolidon(2)yl(l)-2-methoxyaniline.
  • the amino group was replaced according to the Sandmeyer reaction, by a chlorine atom and the product thus formed was nitrated.
  • the chlorine atom was subsequently replaced by a p-tolylthio group with the aid of p-tolylmercaptan.
  • the 4-p-tolylthio S-methoxy-Z-pyrrolidon(2)yl(l)-nitrobenzene thus obtained melts at -l76 C. From this nitro compound the diazonium salt was obtained in the usual way.
  • Example IV Paper consisting as to about 50% of synthetic fibres, which has been precoated with an aqueous dispersion of non-colloidal silica and has then been dried, is sensitized with a liquid containing:
  • the diazotype paper thus obtained contains approximately 0.37 millimol of diazo compound per 111.
  • diazotype paper is imagewise exposed as described in Example II and is then developed with devoloper (B).
  • the copy shows a brown image on a non-stained background.
  • the diazo compound used in the example was prepared as follows: p-aminophenol was brought into reaction with -y-butyrolactone, then nitrated, and alkylated with 2-ethylbutyl bromide to 2-nitro-4-pyrrolidon(2)yl(1)(2-ethylbut)oxy benzene. The nitro group was reduced to an amino group. The latter was acylated wtih phenacetyl chloride. The product thus obtained was nitrated to 4- phenacetylamino--(2' ethylbut)oxy-2-pyrrolidon(2)-yl (1)-nitrobenzene, which melts at 148-151 C. From this nitro compound the diazonium compound was obtained in the usual way.
  • Example V A celluloseacetate film layer of Weight approximately 20 g./m. applied on natural tracing paper of Weight about 80 g./m. is superficially hydrolysed to a depth of about 4 microns and, after removal of the chemicals used for the hydrolysis by washing with Water, is sentitized with a solution of The diazotype material thus obtained contains approximately 0.95 millimol of diazo compound per 111.
  • the diazotype material is imagewise exposed as described in Example 11 and is then developed with developer (B).
  • the copy shows a dark brown image on a clear background.
  • the diazo compound used in the example was prepared as follows: 5-pyrrolidon(2)yl(1)-2-methoxyaniline, HClsalt, was brought into reaction with dicyanodiamide, after which the biguanidino substituent thus introduced was converted with acetic anhydride into a 6-methyl-4,[2]- imino-2,[4]arnino-1H,4H[1H,2H]1,3,5-triazinyl group.
  • Example VI Transparentized paper (grade 506 from Plastic Coating Corporation, Massachusetts, USA.) is sensitized with in 1000 ml. of water and dried.
  • the transparent diazotype paper thus obtained contains approximately 1.18 millimols of diazo compound per m
  • a sheet of the diazotype paper is imagewise exposed underneath a typed letter until all the diazo compound underneath the image-free portions of the letter has bleached out, and is then developed with developer (C).
  • the copy shows a brown azo-dyestutf image on a nonstained background.
  • the azo-dyestuif image has good absorption for ultra-violet radiation, so that the copy is eminently suitable as an intermediate original for making further copies on diazotype material.
  • the diazo compound used in the example was prepared as follows: 5-pyrrolidon(2)yl(l)-2-methoxyaniline was 10 brought into reaction with phosgene and then nitrated, in consequence of which bis-N,N(4-nitro-5-pyrrolidon (2)yl(l)-2-methoxyphenyl)urea was formed, which product melts at 306-307 C. From this bis-nitro compound the bis-diazonium salt was obtained.
  • Example VII White base paper of weight g./m. and suitable for the diazotype process is sensitized with a liquid containing:
  • the diazotype material thus obtained contains approximately 0.45 millimol of diazo compound per m
  • a sheet of the diazotype paper is imagewise exposed underneath a typed letter, until all the diazo compound underneath the image-free portions of the letter has bleached out, and is then developed with developer (C).
  • the copy shows a brown image on a bright white background.
  • the diazo compound used in the example was prepared as follows: p-nitrophenol was chlorinated to 4-nitro-2- chlorophenol. This product was reduced, brought into reaction with y-butyrolactone, and then methylated and nitrated. The 2-pyrrolidon(2)yl)(1)-5-methoxy-4-chloronitrobenzene thus obtained was converted with butylmercaptan into 4-butylthio-5-methoxy-2-pyrrolidon(2)yl (1)-nitrobenzene, which melts at 99 C. From this nitro compound the diazonium salt was obtained in the usual way.
  • Example VIII White base paper of weight 80 g./m. and suitable for the diazotype process is sensitized Wtih a solution of G. Ethane 1,2 dithiol bis -(4' diazo 2' methoxy- 5' pyrrolidon(2)yl(1) phenyl)ether, chlorozincate 25 Tartaric acid 5 Vinnapas H60 30 Sodium naphthalene 1,3,6-trisulfonate 30
  • Example IX White paper of weight g./m.
  • a cellulose acetate film layer (approximately 50% by weight of combined acetic acid) of a thickness of approximately 10 microns, which layer has been afiixed to the paper by means of an adhesive and has been deacetylated to a depth of about 4 microns to an average acetyl content, calculated as combined acetic acid, of 20% by weight (which corresponds to an average number of acyl groups at the OH-groups of 0.7), is coated on the deacetylated side of the cellulose acetate layer with a liquid containing:
  • the layer thus formed is sensitized with a solution of 25 g. of 4-p-tolythi-0-5-methoxy-2-pyrrolidon(2)yl(1)- benzene diazonium chloride, zinc chloride double salt in 500 ml. of ethanol (96%) and 500 m1. of water and dried.
  • the light-sensitive planographic printing plate thus obtained is exposed under a positive original until all the diazo compound underneath the image-free portions of it has bleached out, and the image is subsequently developed by amply wetting the surface of the plate with a liquid which was prepared by dissolving Phloroglucinol 12 Citric acid g 11 Concentrated phosphoric acid ml 87 in 950 ml. of Water and by bringing the pH of this solution up to 7 with a sodium hydroxide solution.
  • the plate After development, the plate is washed and mounted in an offset printer, upon which prints can at once be made from the plate.
  • the background of the plate is bright white and does not absorb fatty printing ink during printing.
  • Example X White baryta-coated paper is sensitized with a solution containing:
  • the diazotype paper thus obtained contains approximately 0.44 millimol of diazo compound per m.
  • a sheet of this paper is imagewise exposed as described in Example II and is developed with developer (A).
  • the copy shows a very dark violet-brown image on a white background.
  • the diazo compound used in the example was prepared as follows: 4-pyrrolidon(2)yl(1)-2-chlorophenol was benzylated, then nitrated and subsequently brought into reaction with benzylmercaptan. The 4-benzylthio-5- benzyloxy 2 pyrrolidon(2)yl(1) nitrobenzene thus obtained melts at 167 C. From this nitro compound the diazonium salt was obtained in the usual Way.
  • Example XI White base paper of weight 80 g./m. and suitable for the diazotype process is coated with a layer by applying approximately g. of a dispersion containing:
  • a light-sensitive layer is formed on the dried layer by applying a liquid containing:
  • the diazotype paper thus obtained contains approximately 0.40 millimol of diazo compound per m.
  • a sheet of it is exposed underneath a transparent ink drawing until all the diazo compound underneath the image-free portions of the drawing has bleached out.
  • the exposed sheet is developed by bringing it into contact with a surface heated to C.
  • the copy shows a violet-red image on a bright white background.
  • the diazo compound used in the example was prepared as'follows:
  • Example XII Sized natural tracing paper is sensitized with a solution containing:
  • the copy shows a red image on a clear background.
  • the diazo compound used in the example was prepared as follows: Z-methylamino-4-nitroanisole was converted with benzoyl chloride into Z-N-methyl-N-benzoylamino-4- nitroanisole. The nitro group of this product was reduced to an amino group, which was brought into reaction with 'y-butyrolactone. The Z-N-methyl-N-benzoylamino-4-pyrrolidon-(2)yl(1)-anisole thus obtained was nitrated to 4- N-methyl-N-benzoylamino-S-methoxy 2 pyrrolidon(2) yl(1)nitrobenzene, which melts at 137 C. From this nitro compound the diazonium salt was obtained in the usual way.
  • Example XIII White base paper of Weight 80 g./m. and suitable for the diazotype process is sensitized with a solution of 4-(4'-methylphenylthio) 5 (4-chlorophenoxy)-2- pyrrolidon(2)yl(1)-benzene diazonium hydrogen sulfate g 25 Tartaric acid g 5 Vinnapas H. 60 ml 30 in 1000 :ml. of water and dried.
  • the diazotype material thus obtained contains approximately 0.40 millimol of diazo compound per m.
  • a sheet of it is imagewise exposed and developed as described in Example V.
  • the copy shows a dark brown image on a bright white background.
  • the diazo compound used in the example was prepared as follows: 3,4-dichloronitrobenzene was fused together with p-chlorophenol and potassium hydroxide. As a result 3-chloro-4-p-chlorophenoxynitrobenzene was proproduced. This product was reduced and then brought into reaction with -butyrolactone.
  • the 4-p-chlorophenoxy-3-chloropyrrolidon(2)yl(1)-benzene was nitrated and converted with p-tolylmercaptan into 4-p-tolylth-io-5-pchlorophenoxy-Z-pyrrolidon (2 yl( 1 -nitrobenzene, which melts at 140-141" C. From this nitro compound the diazonium salt was obtained in the usual way.
  • Diazotype maten'al comprising a support having thereon a light-sensitive layer containing a benzene diazonium salt of the general formula in which X represents an anion, R represents an alkyl, alkenyl, cycloalkyl, aralkyl or aryl group, and Y represents an acylamino, etherified mercapto or dihydro-1,3,5-triazinyl group, or a non-substituted or alkylor alkoxysubstituted phenyl group.
  • R represents a non-branched alkyl group having up to 5 carbon atoms
  • X represents an anion
  • R represents a non-branched alkyl group having up to 5 carbon atoms
  • R represents an alkyl group having up to 4 carbon atoms, a benzyl group or a nonsubstituted or alkylor alkoxy-substituted phenyl group
  • X represents an anion.
  • Diazotype material comprising a support having thereon a light-sensitive layer containing a 4-benzoylamino 2 pyrrolidon(2)yl( 1) 5 methoxy-benzene diazonium salt.
  • Diazotype material comprising a support having thereon a light-sensitive layer containing a 4(4'-methylphenylthio) 2 pyrrolidon(2)yl(1)-5-methoxy-benzene diazonium salt.

Description

Aug. 20, 1968 A. J. J. HENDRICKX LIGHT SENSITIVE DIAZOTYPB MATERIAL AND DIAZONI UM COMPOUNDS THEREFOR Filed Dec. 31, 1964 2 Sheets-Sheet 2 ATTORNEY United States 3,397,985 LIGHT SENSITIVE DIAZOTYPE MATERIAL AND DIAZONIUM COMPOUNDS THEREFOR Andreas Joseph Johannes Hendrickx, Venlo, Netherlands, assignor to Van der Grinten N.V., Northern Limburg, Netherlands Filed Dec. 31, 1964, Ser. No. 422,693 Claims priority, application Netherlands, June 1, 1964, 6406149 9 Claims. (CI. 9691) ABSTRACT OF THE DISCLOSURE The invention relates to diazotype material containing a benzene diazonium salt of a new type and more particularly to one-component diazotype material which is very suitable for development according to the so-called thin layer method with weakly acid 'buifered developing liquids commonly used in the one-component diazotype process.
In this specification reference is made to the structural chemical formula of compounds. These formulae are set out in the accompanying drawings and the references herein are to the figures of these drawings.
Diazotype materials "can be distinguished into: onecomponent diazotype materials, which are developed with the aid of a liquid containing an azo-cou'pling component', two-component diazotype materials, which are developed with the aid of gaseous alkali (ammonia); heat-developable diazotype materials; planographic printing plates sensitized with diazo compounds.
One-component diazotype material is usually developed by spreading (after imagewise exposure) a thin layer (4-12 g./m. of an aqueous developing liquid on the sensitized surface (and also on the non-sensitized surface, if desired).
The developing liquids commonly used in the one-component diazotype process are usually distinguished into alkaline liquids having a pH above 7 and buffered weakly acid liquids the pH of which is between 5.5 and 7. Because of their high keeping quality the weakly acid developers are to be preferred to the alkaline developers. In fact, in diazotype developers phloroglucinol, which in alkaline medium is readily oxidized by the oxygen from the air, is practically always used as azo-coupling component. Developers, both alkaline and buifered Weakly acid developers, which contain phloroglucinol as 2120- coupling component, often in combination with a quantity of resorcinol, are used on a large scale in practice.
In diazotype materials which can be developed with a weakly acid bulfered developer, various diazo compounds derived from hydroquinone dialkyl and diaralkyl ethers and having high coupling activity are employed. Groups of such diazo compounds are: those with the general atent O 3,397,985 Patented Aug. 20, 1968 formula according to FIGURE 1, in which X is an anion, R and R are alkyl or aralkyl groups, R stands for a substituted or a non-substituted alkyl, aralkyl, aryl, alkoxy, aralkoxy, aryloxy, a substituted amidocarbonyl or a substituted amido radical, and R for a hydrogen atom or an alkyl group or is an alkyl or acyl group which forms a heterocyclic ring With N-COR (See: British patent specifications Nos. 347,430, 615,774, 539,031, 510,874, 449,341, 520,304, 620,038, 538,869 and 643,- 309); those with the general formula according to FIGURE -2, in which R, stands for a hydrogen atom, an alkyl, aralkyl, or aryl group '(see: U.S. patent specification No. 2,665,985); those with the general formula according to FIGURE 3, in which R stands for a substituted or a non-substituted alkyl, aralkyl, or aryl group (see: 'Fiat Final Report 813, pages 137 and 138, Dutch patent specification No. 51,536, British patent specification No. 759,045 and German patent specification No. 896,591); and those with the general formula according to FIGURE 4, in which R stands for hydrogen, an acetylamino group, a light alkyl or alkoxy group (see: British patent specification No. 471,614).
The diazo compounds according to the formulae of FIGURES 14 upon exposure yield a somewhat stained photo-decomposition product, so that copies made on a diazotype material sensitized with such a compound show a stained background. When the support of the diazotype material is white paper, the background of the copies instead of being bright white, shows a somewhat dingy stain; when the support is transparent, the copieseven if the azo-dyestuif image has high absorption for ultraviolet radiation-are not very suitable as intermediate originals for making further copies on diazotype material, because the presence of the stained photo-decomposition product in the image-free portions of the intermediate original decreases its transparency to the ultra-violet copying radiation, and thus necessitates a longer exposure time when further copies are to be made.
Dutch patent application No. 288,469, not previously published, describes diazotype material which contains a diazo compound of the general formula according to FIGURE 5, in which X is an anion, R stands for an alkyl, branched alkyl, cycloalkyl, or aralkyl group, CO-R for an acyl radical, R for a substituent from the group formed by acylamido, alkylsulfonamido, aralkylsulfonamido, arylsulfonamido, and triazinyl radicals, and R for an alkyl, branched alkyl, cycloalkyl, aralkyl, or aryl radical.
Dutch patent application No. 295,561, not previously published, described diazotype material which contains a diazo compound of the general formul aaccording to FIGURE 6, in which Xis an anion, R stands for an alkyl, branched alkyl, cycloalkyl, or aralkyl group, COR for an acyl radical, R for a saturated or nonsaturated organic radical, including the cyano radical, and R for an alkyl, branched alkyl, cycloalkyl, aralkyl, or aryl radical.
The diazotype materials according to the Dutch patent applications Nos. 288,469 and 295,561 have a higher developing speed than diazotype material which has been sensitized with a similar diazo compound, derived from hydroquinone, according to the formulae of FIGURES 1-4, and they are often more light-sensitive as Well, particularly when R is a small alkyl group.
The present invention relates to diazotype material characterized in that it contains a diazo compound of the-general 'formula according to FIGURE 7, in which X is an anion, R stands for an alkyl (Le, a non-branched ir branched alkyl), alkenyl, cycloalkyl, aralkyl, or aryl group, and Y for a substituent from the group formed by acylamino, etherified mercapto, dihydrotriazinyl, and substituted or non-substituted phenyl groups.
In this connection by acylamino is to be understood that radical in which R; stands for an organic radical and R for a hydrogen atom, an alkyl or aralkyl group, or for an alkyl or acyl radical which forms a heterocyclic ring with NCOR As compared with diazotype material which has been sensitized with a similar diazo compound derived from hydroquinone, the diazotype material according to the invention shows higher light-sensitivity, while moreover it bleaches out brighter.
As compared with the comparable diazotype materials described in the Dutch patent application Nos. 288,469 and 295,561, the diazotype material according to the invention is a little more light-sensitive and as a rule has better keeping quality. Besides, it bleaches out brighter.
The fact that the diazotype material according to the invention bleaches out bright is manifest when the material, while being printed, has a high moisture content, for instance because it has been kept in a humid atmosphere for some hours. Thus copies made of diazotype paper according to the invention, which has been left unpacked, e.g. for an hour in an ofiice room having a temperature of 20 C. and a relatively humidity of 75% before the copies were made, show a much whiter background than copies on diazotype materials sensitized with diazo compounds according to the formulae of FIGURES 1-6 and stored under the same conditions.
The diazotype material according to the invention is preferably one-component diazotype material. Upon development with weaky acid phloroglucinol developers it yields properly developed copies with strong red to very dark-brown azo-dyestufi images. (Of course, one-component diazotype material according to the invention can be developed with weakly alkaline developing liquids; copies also showing strong, somewhat lighter, red to brown azodyestufis are then obtained). The diazotype material according to the invention may also be heatdevelopable diazotype material.
Whatever may be the composition of the F(nxecoing Whatever may be the composition of the material and the method of development, if the azo-dyestutfs formed upon development are sufliciently oleophilic and if the support has the appropriate constitution the copies can be used as a planographic printing form.
Diazo compounds which can be used in the diazotype material according to the invention are:
4-diazo-2-methoxy-5-pyrrolidon 2)yl( 1 )-N-acetylaniline 4-diazo-2-ethoxy-5-pyrrolidon(2) yl( 1 )-N-ethoxycarb onylaniline 4-diazo-2-benzyloxy-5 -pyrrolidon( 2)yl( l -N-butyrylaniline 4-diazo-2- (4'-ch1orobenzyl oxy-S-pyrrolidon 2) yl( 1)- N-acetylaniline 4-diazo-2-methoXy-5-pyrrolid0n 2) yl( 1 )-N-chloroacetylaniline 4-diazo-2- 2'-ethylbut) oxy-S-pyrrolidon (2) yl( 1 )-N- phenacetylaniline 4-diazo-2-methoXy-5 -pyrro1idon(2 yl 1 )-N- benzoylaniline S-methoxy-2,4-di-pyrrolidon (2 yl 1)-diazobenzene 4-diazo2-methoxy-5-pyrrolidon(2)yl(1)-N-methyl- N-benzoylaniline 4-diazo-2-ethoxy-5-pyrrolidon (2 yl 1 )-N- benzoylaniline 4-diazo-2-n-propoxy-5-pyrrolidon(2 yl( l -N- benzoylaniline 4-diazo-2-n-butoxy-5-pyrrolidon(2)yl(1)-N- benzoylaniline 4-diazo-2-isoamyloxy-S-pyrrolidon( 2 yl( 1 )-N- benzoylaniline Y 4-diazo-2- 2-hydroxyethyl oxy-S-pyrrolidon (2 yl( 1)- N-benzoylaniline 4-diazo-2-ethoxyethoxy-5-pyrrolidon (2 )yl( 1 )-N- benzoylaniline 4-diazo-2-( 2'-diethylaminoeth) oxy-S-pyrrolidon (2 yl( l )-N-benzoylaniline 4-diazo-2- 4'-chlorophen oxy-S-pyrrolidon (2 yl( 1 N-benzoylaniline 4-diazo-2-allyloxy-S-pyrrolidbn( 2)yl( l -N- benzoylaniline 4-diazo-2-cyclopentoxy-pyrrolidon 2 )yl( l )-N- benzoylaniline bis-N,N-4'-diazo-2'-methoxy-5- pyrrolidon 2 yl( 1 )-phenyl urea 1- (4-diazo-2'methoxy-5 -pyrrolidon 2 yl 1 phenyl -4 [2] -amino-2- [4] -imino-6-rnethyl- 1H,2H[1H,4H] 1,3,5 -triazine 4-diazo-2-methoxy-5 -pyrrolidon (2 yl( 1)- phenylthiomethyl ether 4-diazo-2-ethoxy-S-pyrrolidon (2 yl( 1 phenylthiomethyl ether 4-diazo-2-n-propoxy-S-pyrrolidon (2 )yl( 1 phenylthiomethyl ether 4-diazo-2-n-but0xy-S-pyrrolidon( 2 yl l phenylthiomethyl ether 4-diazo-2-methoxy-S-pyrrolidon 2 yl( l phenylthioethyl ether 4-diazo-2-ethoxy-5-pyrrolidon( 2 yl( l )-phenylthioethyl ether 4-diazo-2-n-propoxy-S-pyrrolidon 2 yl 1)- phenylthioethyl ether 4-diazo-2-ally1oxy-5 -pyr-rolidon (2 )yl( l phenylthioethyl ether 4-diazo-2-n-butoxy-5-pyrrolidon (2 yl( 1)- phenylthioethyl ether 4-diazo-2- (4'-chlorophen oxy-S -pyrrolidon 2) yl( 1 phenylthioethyl ether 4-diazo-2-cyclopentoxy-S-pyrrolidon(2)yl(1)- phenylthioethyl ether 4-diazo-2-methoxy-ipyrrolidon(2) yl( l phenylthiobutyl ether 4-diazo-2-(2'-ethylbut) oxy-S-pyrrolidon (2 yl( l phenylthiocar-boxymethyl ether 4-diazo-2-benzyloxy-S-pyrrolidon (2)yl( 1)- phenylthiobenzyl ether ethanedithiol-(1,2)-bis(4-diazo-2-meth0xy-5 pyrrolidon (2 yl( 1 )-phenyl ether 4-diazo-2-methoxy-5-pyrrolidon (2 yl( l )-pheny1thiop-tolyl ether 4-diazo-2-ethoxy-5 -pyrrolid on 2 yl( 1 -phenylthiop-tolyl ether 4-diazo-2-n-propoxy-5-pyrrolidon 2) yl 1 -phenylthiop-tolyl ether 4-diazo-2-n-butoxy-5-pyrrolidon (2 yl( l phenylthio-p-tolyl ether 4-diazo-2- (4'-chlorophen oxy-S-pyrrolidon 2 yl( 1 phenylthio-ptolyl ether 4-diazo-2-methoxy-S-pyrrolidon 2) yl 1 .-diphenyl 4-diazo-2-ethoxy-5-pyrrolidon (2 )yl( l )-diphenyl 4-diazo-2-n-propoxy-S-pyrrolidon (2 )yl( l)- diphenyl 4-diazo-2-n-butoXy-5 -pyrroli don 2) yl 1 diphenyl 4-diazo-2-cyclopentoxy-S-pyrrolidon (2 yl 1)- diphenyl 4-diazo-2,4'-dimethoxy-5-pyrrolidon 2 yl( 1)- diphenyl 4-diazo-2-n-butoxy-4-methoxy-5-pyrrolidon(2 yl 1 diphenyl.
The diazo compounds are used as diazonium salts, for instance as chlorides or sulfates, or as diazonium metal double salts, such as the zinc chloride double salt, the manganese chloride double salt, and the stannic chloride double salt, or as borofluorides. They can be applied separately, mixed together, or in admixture with diazo compounds of other types. It is obvious that, when mixtures are used, the effect of the new diazo compounds will be smaller according as a larger quantity of the other compound(s) is used.
Although the diazo compounds according to the invention have high coupling activity and good light-sensitivity, moreover bleach out while forming practically colourless photo-decomposition products, and yield highcontrast azo-dyestuffs with the conventional azocoupling components, such as phloroglucinol and resorcinol, nevertheless there are differences in qualities and accessibility between the various diazo compounds.
Because of their ready accessibility, their comparatively very high coupling activity, and their relatively high stability, the diazo compounds having a benzoylamino or an etherified mercapto group in para-position relative to the diazo group are preferred. Diazotype materials which have good keeping quality, develop very rapidly, and are reasonably inexpensive can be prepared with these diazo compounds.
Very useful compounds are, for instance, those of the general formula according to FIGURE 8 in Which R represents a non-branched alkyl group having up to 5 carbon atoms and X represents an anion.
Particularly valuable diazo compounds are those with an alkyl, aralkyl, or arylthio group in para-position and more especially those of the general formula according to FIGURE 9, in which R represents a non-branched alkyl group having up to 5 carbon atoms, R represents a non-branched alkyl group having up to 4 carbon atoms or a substituted or non-substituted benzyl or phenyl group, and X represents an anion.
Diazotype material sensitized therewith has. higher light-sensitivity than diazotype material according to the invention containing a diazo compound with another substituent in para-position.
In the diazotype material according to the invention, the support to be used may be paper, printing-plate paper, tracing paper, transparentized paper, linen, tracing linen, synthetic paper, film material, such as films of cellulose acetate and polyester, metal, e.g. planographic printing plates of aluminium.
Furthermore the diazotype material according to the invention may contain the additions commonly used in the diazotype process, e.g. acids, such as citric acid, tartaric acid, and boric acid; stabilizers, such as benzene and naphthalene sulfonic acids and their water-soluble salts, e.g. sodium napthalene 1,3,6-trisulfonate; metal salts, such as zinc chloride, magnesium chloride, nickel sulfate, and alum; surface-improving substances, such as finely divided silica (colloidal or non-colloidal), aluminium oxide, barium sulfate, rice starch, etc.; binders, such as gelatin, gum arabic, cellulose ethers, starch derivatives, polyvinyl alcohol; dispersions of synthetic resins, such as dispersions of polyvinyl acetate in aqueous media containing cationic, non-ionic or anionic dispersing agents.
The phloroglucinol developers which are used in the one-component diazotype process often vary as to their composition and acidity. Below three weakly acid phloroglucinol developers employed in practice are described. These developers will be used for development in the following examples.
Developer A is a solution of:
Phloroglucinol g .4 Acetoacetanilide 0.1 2-ethyl-1-hexanol sulfate Tergitol 08 (from Union Carbide & Carbon Corp., New York 17, U.S.A.;
Tergitol is a registered trademark) 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 butylnaphthalene sulfonate Sorbit P (from Geigy Chem. Corp. Ardsley, N.Y., U.S.A.; the
word Sorbit is a registered trademark) 2 Sodium formate 14 Sodium benzoate 22 Trisodium citrate (2 aq.) 49 Citric acid 1.2
in 1000 ml. of water.
The pH of this liquid is 6.5.
Developer C is a solution of:
Phloroglucinol g- 5 Resorcinol g 1 Dipotassium phosphate 3 Tergitol 08 ml 3 Maleic anhydride g 52 Potassium hydroxide solution (13.5 N) ml 75 in 1000 ml. of Water.
The pH of this liquid is 6.9.
In addition to phloroglucinol (and in addition to, or instead of, resorcinol), the weakly acid buffered developers may also contain other azo-coupling components having high coupling activity, e.g. 2,3 dihydroxynaphthalene, and acetoacetanilide. The following examples will serve to illustrate the invention:
Example I Three sensitizing liquids are prepared: (A) A liquid containing:
G. 4-benzoylamino 2 pyrrolidon(2)yl(1)-5-methoxybenzene diazonium chloride, zinc chloride double salt 16.6 Tartaric acid 5 Saponin 3 in 1000 ml. of water.
(B) A similar liquid to that mentioned under (A), but containing, instead of the 4-benzoylamino-2-pyrrolidon- (2)yl(1)-5- methoxybenzene diazonium salt, and equimolar quantity of 4-benzoylamino-2-N-methyl-N-acetylamino-Sanethoxy benzene diazonium chloride, zinc chloride double salt.
(C) A similar liquid to that mentioned under (A), but containing, instead of the said diazonium salt, an equimolar quantity of 4-benzoylamino-2,S-dimethoxybenzene diazonium chloride, zinc chloride double salt.
With each of these liquids a sheet of white base paper of weight g./m. and suitable for the diazotype process is sensitized. After sensitization the three sheets are dried. Each sheet contains approximately 0.40 millimol of diazo compound per m A strip of each sheet is imagewise exposed underneath a transparent ink drawing for the time required to bleach out, on the strip of sheet (A), all the diazo compound underneath the image-free portions of the original. After this, the strips are developed with developer (A).
Strip (A) shows a violet-brown image on a bright white background. Strip (B) shows a dark brown image on a somewhat foggy background, and strip (C) shows a black image on a heavy violet-grey background.
A second strip of the sheets (A), (B) and (C), screened from the light, is kept for an hour in a room having a relative humidity of 75% and a temperature of approximately 20 C. The strips are then fed, together with a transparent ink rdrawing, through a continuously operating exposure apparatus for the diazotype process comprising an exposure cylinder of glass which has a surface temperature of approximately 60 C. and in which a high-pressure mercury vapour lamp is mounted, with such a speed that, on strip (C), all the diazo compound underneath the image-free portions of the drawing has bleached out.
The strips are then developed with developer (A). It is clearly visible that the white background of the strips (B) and (C) is less white than that of strip (A).
The 2-pyrrolidon(2)yl(1) diazo compound used in the example was prepared as follows: p-aminophenol was brought into reaction with -butyrolactone. Thus 4-pyrrolidon(2)yl(1)phenol was formed, which product was nitrated and then methylated with dimethyl sulfate. The nitro group was reduced to an amino group and the amino group was benzoylated. The 4-pyrrolidon(2)yl(l)-2- benzoylaminoanisole was nitrated to 4-pyrrolidon(2)yl- (1)-2-benzoylamino-S-nitroanisole, which melts at 223- 225 C. Upon reduction, 4-benzoylamino-Z-pyrrolidon- (2)yl(l)-5-methoxyaniline was formed, which product was diazotizecl. The diazo compound was obtained in the form of the chlorozincate.
EXAMPLE II White base paper of weight 80 g./m. and suitable for the diazotype process is sensitized with a liquid containing:
4 phenyl 2 pyrrolidon(2)yl( l )-5-methoxybenzene diazonium chloride, zinc chloride double salt Tartaric acid 5 Saponin 3 in 1000 ml. of Water and dried.
The diazotype paper thus obtained contains approxi n1ately 0.45 millimol of diazo compound per m2. A sheet of the diazotype paper is imagewise exposed underneath a transparent ink drawing until all the diazo compound underneath the image-free portions of the drawing has bleached out, and is then developed with developer (A).
The copy shows a red image on a bright White background.
When the above-mentioned sensitizing liquid contains, instead of the said diazo compound, an equimolar quantity of the diazo compound 4-phenyl-2,S-dimethoxybenzene diazonium chloride, zinc chloride double salt, the diazotype paper thus obtained is considerably less light-sensitive, and gives copies with a black azo-dye-stuff image on a background having a somewhat dingy stain.
The diazo compound used in the example was prepared as follows: 2-hydroxybiphenyl was methylated and then nitrated. The nitro group of the 2-methoxy-5-nitrobiphenyl was reduced and the amino group thus obtained was brought into reaction with -butyrolactone. The 2-phenyl- 4-pyrrolidon(2)yl(l)anis0le thus prepared was nitrated to 4 phenyl-2-pyrrolidon(2)yl(l)-5-methoxynitrobenzene, which melts at 123 C. From this nitro compound the di azo compound was prepared by reduction and diazotization; it was obtained in the form of the chlorozincate.
8 Example III Three sensitizing liquids are prepared: (A) A liquid containing:
4 (4 methylphenylthio) 2-pyr rolidon (2 -yl 1 -5-G. methoxybenzene diazonium chloride, zinc chloride double salt 16 Tartaric acid 5 Saponin 3 in 1000 ml. of water.
(B) A similar liquid to that mentioned under (A), but containing, instead of the said diazo compound, an equimolar quantity of 4-(4-methylphenylthio)-2-Nmethyl-N- ethoxycarbonylamino-S-methoxybenzene diazonium chloride, zinc chloride double salt.
(C) A similar liquid to that mentioned under (A), but containing, instead of the said diazo compound, an equimolar quantity of 4-(4-methylphenylthio)-2,5-dimethoxybenzene diazonium chloride, zinc chloride double salt.
With each of these liquids a sheet of white base paper of weight g./m. and suitable for the diazotype process is sensitized. After sensitization the three sheets are dried. Each sheet contains approximately 0.37 millimol of diazo compound per m.
A strip of each sheet is imagewise exposed underneath a transparent ink drawing for the time required to bleach out on the strip of sheet (A), all the diazo compound onderneath the image-free portions of the original. After this, the strips are developed with developer (B).
Strip (A) shows a brown image on a bright white background. Strip (B) shows a dark brown image on a somewhat foggy light brown background. Strip (C) shows a green-black image on a heavily foggy grey background.
A second strip of the sheets (A), (B), and (C), screened from the light, is stored for an hour in a room with a relative humidity of 75% and a temperature of approximately 20 C. The strips are then fed, together with a transparent ink drawing, through a continuously operating exposure apparatus for the diazotype process with an exposure cylinder of glass which has a surface temperature of approximately 60 C. and in which a high-pressure meroury vapour lamp is mounted, with such a speed that on strip (C) all the diazo compound underneath the imagefree portions of the drawing has bleached out.
The strips are then developed with developer (B). The white background of the strips (B) and (C) is far less white than that of strip (A).
The diazo compound with the 2-pyrrolidon(2)yl(l) group used in the example was prepared as follows: 4-pyrrolidon(2)yl(l) 2 nitroanisole was reduced to 5-pyrrolidon(2)yl(l)-2-methoxyaniline. The amino group was replaced according to the Sandmeyer reaction, by a chlorine atom and the product thus formed was nitrated. The chlorine atom was subsequently replaced by a p-tolylthio group with the aid of p-tolylmercaptan. The 4-p-tolylthio S-methoxy-Z-pyrrolidon(2)yl(l)-nitrobenzene thus obtained melts at -l76 C. From this nitro compound the diazonium salt was obtained in the usual way.
Example IV Paper consisting as to about 50% of synthetic fibres, which has been precoated with an aqueous dispersion of non-colloidal silica and has then been dried, is sensitized with a liquid containing:
4 phenacetylamino 2 pyrrolidon(2)yl(l)-5-(2'- ethylbut)oxy benzene diazonium chloride, zinc chloride double salt 22 Tartaric acid 5 Saponin 3 in 1000 ml. of water and dried.
The diazotype paper thus obtained contains approximately 0.37 millimol of diazo compound per 111. The
diazotype paper is imagewise exposed as described in Example II and is then developed with devoloper (B).
The copy shows a brown image on a non-stained background.
The diazo compound used in the example was prepared as follows: p-aminophenol was brought into reaction with -y-butyrolactone, then nitrated, and alkylated with 2-ethylbutyl bromide to 2-nitro-4-pyrrolidon(2)yl(1)(2-ethylbut)oxy benzene. The nitro group was reduced to an amino group. The latter was acylated wtih phenacetyl chloride. The product thus obtained was nitrated to 4- phenacetylamino--(2' ethylbut)oxy-2-pyrrolidon(2)-yl (1)-nitrobenzene, which melts at 148-151 C. From this nitro compound the diazonium compound was obtained in the usual way.
Example V A celluloseacetate film layer of Weight approximately 20 g./m. applied on natural tracing paper of Weight about 80 g./m. is superficially hydrolysed to a depth of about 4 microns and, after removal of the chemicals used for the hydrolysis by washing with Water, is sentitized with a solution of The diazotype material thus obtained contains approximately 0.95 millimol of diazo compound per 111. The diazotype material is imagewise exposed as described in Example 11 and is then developed with developer (B).
The copy shows a dark brown image on a clear background.
The diazo compound used in the example was prepared as follows: 5-pyrrolidon(2)yl(1)-2-methoxyaniline, HClsalt, was brought into reaction with dicyanodiamide, after which the biguanidino substituent thus introduced was converted with acetic anhydride into a 6-methyl-4,[2]- imino-2,[4]arnino-1H,4H[1H,2H]1,3,5-triazinyl group. The compound thus obtained Was nitrated at 4,6'-methyl- 4'-[2'] imino 2'[4']-amino-lH,4H[1H,2'H]-1',3',5- triazinyl(l) 2 pyrrolidon(2)yl(1)-5-methoxynitrobenzene which melts at 242 C. From this nitro compound the diazonium salt was obtained in the usual way.
Example VI Transparentized paper (grade 506 from Plastic Coating Corporation, Massachusetts, USA.) is sensitized with in 1000 ml. of water and dried.
The transparent diazotype paper thus obtained contains approximately 1.18 millimols of diazo compound per m A sheet of the diazotype paper is imagewise exposed underneath a typed letter until all the diazo compound underneath the image-free portions of the letter has bleached out, and is then developed with developer (C).
The copy shows a brown azo-dyestutf image on a nonstained background. The azo-dyestuif image has good absorption for ultra-violet radiation, so that the copy is eminently suitable as an intermediate original for making further copies on diazotype material.
The diazo compound used in the example was prepared as follows: 5-pyrrolidon(2)yl(l)-2-methoxyaniline was 10 brought into reaction with phosgene and then nitrated, in consequence of which bis-N,N(4-nitro-5-pyrrolidon (2)yl(l)-2-methoxyphenyl)urea was formed, which product melts at 306-307 C. From this bis-nitro compound the bis-diazonium salt was obtained.
Example VII White base paper of weight g./m. and suitable for the diazotype process is sensitized with a liquid containing:
4 diazo 2 methoxy 5 pyrrolidon(2)yl(l)phenylthio-n buty1 ether, chlorozincate g 20 Tartaric acid -g 5 Sodium naphthalene 1,3,6-trisulfonate -g 30 Vinnapas H.60 (polyvinyl acetate dispersion from Wacker Chemie G.m.b.H., Munich, Germany; Vinnapas is a registered trademark) ml 30 in 1000 ml. of water and dried.
The diazotype material thus obtained contains approximately 0.45 millimol of diazo compound per m A sheet of the diazotype paper is imagewise exposed underneath a typed letter, until all the diazo compound underneath the image-free portions of the letter has bleached out, and is then developed with developer (C).
The copy shows a brown image on a bright white background.
The diazo compound used in the example was prepared as follows: p-nitrophenol was chlorinated to 4-nitro-2- chlorophenol. This product was reduced, brought into reaction with y-butyrolactone, and then methylated and nitrated. The 2-pyrrolidon(2)yl)(1)-5-methoxy-4-chloronitrobenzene thus obtained was converted with butylmercaptan into 4-butylthio-5-methoxy-2-pyrrolidon(2)yl (1)-nitrobenzene, which melts at 99 C. From this nitro compound the diazonium salt was obtained in the usual way.
Example VIII White base paper of weight 80 g./m. and suitable for the diazotype process is sensitized Wtih a solution of G. Ethane 1,2 dithiol bis -(4' diazo 2' methoxy- 5' pyrrolidon(2)yl(1) phenyl)ether, chlorozincate 25 Tartaric acid 5 Vinnapas H60 30 Sodium naphthalene 1,3,6-trisulfonate 30 Example IX White paper of weight g./m. coated on one side with a cellulose acetate film layer (approximately 50% by weight of combined acetic acid) of a thickness of approximately 10 microns, Which layer has been afiixed to the paper by means of an adhesive and has been deacetylated to a depth of about 4 microns to an average acetyl content, calculated as combined acetic acid, of 20% by weight (which corresponds to an average number of acyl groups at the OH-groups of 0.7), is coated on the deacetylated side of the cellulose acetate layer with a liquid containing:
Titanium dioxide with a particle size of approximately 0.2 micron g 13 Hydroxyethylcellulose Cellosize WP-09 (from Union Carbide Corp. of U.S.A g 27 Glyoxal g 4 Ethanol (96%) ml 8 Water ml 92 and dried at 110 C. during 50 seconds.
The layer thus formed is sensitized with a solution of 25 g. of 4-p-tolythi-0-5-methoxy-2-pyrrolidon(2)yl(1)- benzene diazonium chloride, zinc chloride double salt in 500 ml. of ethanol (96%) and 500 m1. of water and dried.
The light-sensitive planographic printing plate thus obtained is exposed under a positive original until all the diazo compound underneath the image-free portions of it has bleached out, and the image is subsequently developed by amply wetting the surface of the plate with a liquid which was prepared by dissolving Phloroglucinol 12 Citric acid g 11 Concentrated phosphoric acid ml 87 in 950 ml. of Water and by bringing the pH of this solution up to 7 with a sodium hydroxide solution.
After development, the plate is washed and mounted in an offset printer, upon which prints can at once be made from the plate.
The background of the plate is bright white and does not absorb fatty printing ink during printing.
Example X White baryta-coated paper is sensitized with a solution containing:
4 benzylthio benzyloxy 2 pyrrolidon(2)yl (l)-benzene diazonium chloride, zinc chloride double salt g 18 Tartaric acid g 5 The aqueous 40% solution of sodium xylene sulfonate Naxonad 4 L (from Nease Chemical Company, Lock Haven, Pa., U.S.A.) ml 5 Ethanol (96%) ml 500 Water ml 500 and dried.
The diazotype paper thus obtained contains approximately 0.44 millimol of diazo compound per m. A sheet of this paper is imagewise exposed as described in Example II and is developed with developer (A).
The copy shows a very dark violet-brown image on a white background.
The diazo compound used in the example was prepared as follows: 4-pyrrolidon(2)yl(1)-2-chlorophenol was benzylated, then nitrated and subsequently brought into reaction with benzylmercaptan. The 4-benzylthio-5- benzyloxy 2 pyrrolidon(2)yl(1) nitrobenzene thus obtained melts at 167 C. From this nitro compound the diazonium salt was obtained in the usual Way.
Example XI White base paper of weight 80 g./m. and suitable for the diazotype process is coated with a layer by applying approximately g. of a dispersion containing:
Di(octadecylammonium)oxalate 115 Hydrolysed potato starch, Farinex T.S.D. (from Nationale Zetmeelindustrie N.V., Veendam, Netherlands) Gum arabic 7.5
Oxalic acid, 21-1 0 2.5
12 in 1000 ml. of water and dried.
A light-sensitive layer is formed on the dried layer by applying a liquid containing:
4 methylthio 2 pyrrolidon(2)yl (l) 5 methoxybenzene diazonium chloride, zinc chloride double salt 7 7'-hydroxy-1',2',4,5-naphthimidazole 20 Tartaric acid 22.5 Gum arabic 7.5 Farinex T.S. D. 35 Di(octadecylammonium)oxalate in 1000 ml. of water and drying.
The diazotype paper thus obtained contains approximately 0.40 millimol of diazo compound per m. A sheet of it is exposed underneath a transparent ink drawing until all the diazo compound underneath the image-free portions of the drawing has bleached out. The exposed sheet is developed by bringing it into contact with a surface heated to C.
The copy shows a violet-red image on a bright white background.
The diazo compound used in the example was prepared as'follows:
5 pyrrolidon(2)yl(l)-4-nitro-2-methoxychlorobenzene (see Example III) was brought into reaction with methylmercaptan. The 4-methylthio-5-methoxy-2-pyrrolidon(2)- yl(l)-nitrobenzene thus obtained melts at l37-l38 C. From this nitro compound the diazonium salt was obtained in the usual way.
Example XII Sized natural tracing paper is sensitized with a solution containing:
4-N-methyl-N-benzoylamino 5 methoxy-2-pyrrolidon(2)yl(1)-benzene diazonium chloride, zinc chloride double salt g 21 Tartaric acid g 5 Ethanol (96%) ml 100 Water ml 900 and dried The transparent diazotype paper thus obtained contains approximately 0.63 millimol of diazo compound per m A sheet of this paper is imagewise exposed as described in Example I and is then developed with developer (B).
The copy shows a red image on a clear background.
The diazo compound used in the example was prepared as follows: Z-methylamino-4-nitroanisole was converted with benzoyl chloride into Z-N-methyl-N-benzoylamino-4- nitroanisole. The nitro group of this product was reduced to an amino group, which was brought into reaction with 'y-butyrolactone. The Z-N-methyl-N-benzoylamino-4-pyrrolidon-(2)yl(1)-anisole thus obtained was nitrated to 4- N-methyl-N-benzoylamino-S-methoxy 2 pyrrolidon(2) yl(1)nitrobenzene, which melts at 137 C. From this nitro compound the diazonium salt was obtained in the usual way.
Example XIII White base paper of Weight 80 g./m. and suitable for the diazotype process is sensitized with a solution of 4-(4'-methylphenylthio) 5 (4-chlorophenoxy)-2- pyrrolidon(2)yl(1)-benzene diazonium hydrogen sulfate g 25 Tartaric acid g 5 Vinnapas H. 60 ml 30 in 1000 :ml. of water and dried.
The diazotype material thus obtained contains approximately 0.40 millimol of diazo compound per m. A sheet of it is imagewise exposed and developed as described in Example V.
The copy shows a dark brown image on a bright white background.
The diazo compound used in the example was prepared as follows: 3,4-dichloronitrobenzene was fused together with p-chlorophenol and potassium hydroxide. As a result 3-chloro-4-p-chlorophenoxynitrobenzene was proproduced. This product was reduced and then brought into reaction with -butyrolactone. The 4-p-chlorophenoxy-3-chloropyrrolidon(2)yl(1)-benzene was nitrated and converted with p-tolylmercaptan into 4-p-tolylth-io-5-pchlorophenoxy-Z-pyrrolidon (2 yl( 1 -nitrobenzene, which melts at 140-141" C. From this nitro compound the diazonium salt was obtained in the usual way.
What I claim is:
1. Diazotype maten'al comprising a support having thereon a light-sensitive layer containing a benzene diazonium salt of the general formula in which X represents an anion, R represents an alkyl, alkenyl, cycloalkyl, aralkyl or aryl group, and Y represents an acylamino, etherified mercapto or dihydro-1,3,5-triazinyl group, or a non-substituted or alkylor alkoxysubstituted phenyl group.
2. One-component diazotype material according to claim 1, wherein Y is a benzoylamino radical.
3. One-component diazotype material according to claim 1, wherein Y represents an alkyl-thio, aralkyl-thio or aryl-thio 'group.
4. A diazo compound of the general formula l r-CH:
in which R represents a non-branched alkyl group having up to 5 carbon atoms, and X represents an anion.
14 5. A diazo compound of the general formula NzX | CHg-CH:
C- Hg R10 II o in which R represents a non-branched alkyl group having up to 5 carbon atoms, R represents an alkyl group having up to 4 carbon atoms, a benzyl group or a nonsubstituted or alkylor alkoxy-substituted phenyl group, and X represents an anion.
6. Diazotype material comprising a support having thereon a light-sensitive layer containing a 4-benzoylamino 2 pyrrolidon(2)yl( 1) 5 methoxy-benzene diazonium salt.
7. A 4-benzoylamino-2-pyrrolidon(2)yl(1)-5-methoxybenzene diazonium salt.
8. Diazotype material comprising a support having thereon a light-sensitive layer containing a 4(4'-methylphenylthio) 2 pyrrolidon(2)yl(1)-5-methoxy-benzene diazonium salt.
9. A 4- (4-methylphenylthio -2-pyrrolidon(2)yl( 1 )-5- methoxy-benzene diazonium salt.
References Cited UNITED STATES PATENTS 2,286,701 6/ 1942 Werner 9691 2,456,514 12/ 1948 Johnston 9691 2,665,985 1/1954 Sus 96--91 3,016,298 1/1962 Sanders et al 96--91 XR 3,155,512 11/1964 De Boer 9691 3,338,713 8/1967 Hendrickx et al. 96-91 FOREIGN PATENTS 538,869 8/ 1941 Great Britain.
OTHER REFERENCES Brown, D. J.: Chem. Ind., 22 (1944), pp. 146-148.
NORMAN G. TORCHIN, Primary Examiner. C. L. BOWERS, Assistant Examiner.
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3547637A (en) * 1966-07-06 1970-12-15 Keuffel & Esser Co Light-sensitive diazotype material
US3868255A (en) * 1969-07-23 1975-02-25 Gaf Corp Diazonium salts and diazotype materials
US3970460A (en) * 1973-03-28 1976-07-20 Multitec Ag Diazotype composition
US4267249A (en) * 1978-08-22 1981-05-12 Aerni-Leuch Ag Benzene diazonium salts and diazotype material utilizing same
US4520094A (en) * 1981-10-21 1985-05-28 Hitachi, Ltd. Process for forming powder pattern on light exposed layer having photosensitive diazonium salts
US5998082A (en) * 1996-08-26 1999-12-07 Fuji Photo Film Co., Ltd. Thermal recording material

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2618429A1 (en) * 1987-07-24 1989-01-27 Centre Nat Rech Scient NEW BIFUNCTIONAL PHOTOACTIVABLE REAGENTS, THEIR PREPARATION AND THEIR APPLICATION

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GB538869A (en) * 1940-01-11 1941-08-20 Humphrey Desmond Murray Improvements in light-sensitive diazo compounds
US2286701A (en) * 1939-06-08 1942-06-16 Kalle & Co Ag Diazotype printing material
US2456514A (en) * 1945-09-07 1948-12-14 Bruning Charles Co Inc Diazotype light-sensitive materials
US2665985A (en) * 1949-10-26 1954-01-12 Keuffel & Esser Co Light-sensitive diazo compounds and photoprint material prepared therefrom
US3016298A (en) * 1957-06-17 1962-01-09 Grinten Chem L V D One-component diazotype material
US3155512A (en) * 1960-06-27 1964-11-03 Lichtdrukpapierfabriek De Atla Light-sensitive diazotype compositions
US3338713A (en) * 1963-02-01 1967-08-29 Grinten Chem L V D Diazotype material

Patent Citations (7)

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Publication number Priority date Publication date Assignee Title
US2286701A (en) * 1939-06-08 1942-06-16 Kalle & Co Ag Diazotype printing material
GB538869A (en) * 1940-01-11 1941-08-20 Humphrey Desmond Murray Improvements in light-sensitive diazo compounds
US2456514A (en) * 1945-09-07 1948-12-14 Bruning Charles Co Inc Diazotype light-sensitive materials
US2665985A (en) * 1949-10-26 1954-01-12 Keuffel & Esser Co Light-sensitive diazo compounds and photoprint material prepared therefrom
US3016298A (en) * 1957-06-17 1962-01-09 Grinten Chem L V D One-component diazotype material
US3155512A (en) * 1960-06-27 1964-11-03 Lichtdrukpapierfabriek De Atla Light-sensitive diazotype compositions
US3338713A (en) * 1963-02-01 1967-08-29 Grinten Chem L V D Diazotype material

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3547637A (en) * 1966-07-06 1970-12-15 Keuffel & Esser Co Light-sensitive diazotype material
US3868255A (en) * 1969-07-23 1975-02-25 Gaf Corp Diazonium salts and diazotype materials
US3970460A (en) * 1973-03-28 1976-07-20 Multitec Ag Diazotype composition
US4267249A (en) * 1978-08-22 1981-05-12 Aerni-Leuch Ag Benzene diazonium salts and diazotype material utilizing same
US4520094A (en) * 1981-10-21 1985-05-28 Hitachi, Ltd. Process for forming powder pattern on light exposed layer having photosensitive diazonium salts
US5998082A (en) * 1996-08-26 1999-12-07 Fuji Photo Film Co., Ltd. Thermal recording material

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ES308000A1 (en) 1965-04-16
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DE1472798C3 (en) 1975-09-25
NL6406149A (en) 1965-12-02
LU47720A1 (en) 1965-03-04
DE1472798B2 (en) 1973-02-15
NL133921C (en) 1972-04-17
DK114674B (en) 1969-07-21
BE657907A (en) 1965-07-05
GB1064129A (en) 1967-04-05
FR1422456A (en) 1965-12-24

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