[1]3 @ 3 1 1 , 4 7 5 Un'lted States Patent Office Patented Mar. 28, 1967 1 2 3,311,475 DIAZOTYPE MATERIAL Arie van Loon and Bernardus Hubertus Huibers, Venlo, Netherlands, assignors to Chemische Fabriek L. van der Grinten N.V., Venlo, Netherlands, a corporation 5 of Dutch law No Drawing. Ffled July 14, 1964, Ser. No. 382,637 Claims priority, application Netherlands, July 19, 1963, 295,561 15 Claims. (Cl. 96- 91) 10 This invention relates to a new class of diazonium compounds and to diazotype materials and diazotype processes which make use of such compounds. This diazotype material may, for instance be so-called one-component diazotype material wherein the material contains the diazonium 1 5 compound and is developed with a liquid developer containin.- an,azo coupling component, or so-called two component diazotype material wherein the material contains both the diazonium compound and the azo coupling component and is developed with the aidof ammonia vapour, 20 or diazotype 1-naterial which is developed by heat treatment. In Fiat Final Report 813, pages 137 and 138, and Dutch patent specification No. 51,536 (corresponding to U.S. Patent No. 2,286,701), several 4-diazo-2,5-dialkoxy25 phenylthioalkyl, -cycloalkyl, -aralkyl, and -aryl ethers for the sensitizin- of diazotype materials are described. However, only the 4-diazo-2,5-dialkoxyphenylthioaryl, ethers, particularly the 4-diazo-2,5-dimethoxy- and diethoxyphenylthio (o and p) tolyl ethers, have proved to be of 30 practical value (compare British patent specification No. 759,045 and German patent specification No. 896,591). One-component diazotype material sensitized with such compounds furnishes copies showing fine black azodyestuff images upon imagewise exposure and development 3 5 according to the so-called thin-layer method by means of buffered weakly acid phloroglucinol develope@rs, which are very attractive because of their high keeping quality. (Irl the thin-layer method a very thin layer of a develop@ 4 0 in@ solution is applied to the exposed diazotype material.) H@wever, the azo-dyestuffs thus obtained b-ave only low absorption f<)r radiation in the near ultra-violet part of the spectrum, the radiation with the aid of which copies are made in the diazo-type process. In consequence, copies on translucent diazotype materials, sensitized with 45 such diazo compounds,:are not very suitable, if at all, for use as so-called intermediate copies from which further copies are made. Jud,--,d by modern standards, diazotype materials sensi- 50 tized with the 4-diazo-2,5-dialkoxyphenylthiotoJyl ethers have moderate li,@ht-sensitivity. Moreover, using weakly acid phloro,-Iucinol developers such one-component diazotype material often develops too slowly, particularly when the copy is not heated after the application of the 55 developing liquid. According to a first feature of the present invention there are provided diazonium compounds of the general formula: N2@X 6 0 / RI N \ CO-R2 R40 1 6 ,5 -U3 in which X represents an anion, RI represents an alkyl, branched alkyl, cycloalkyl or aralkyl radical, CO-R2 rep- 70 resents an acyl radical, R2 being hydrogen or an organic radical, R3 represents a saturated or unsaturated organic radical or a eyano croup, and R4 represents an alkyj, branched alkyl, cycloalkyl, aralkyl, or aryl radical. The foregoing diazonium compounds in diazotype mate-rial have the advantages that they develop much more rapidly than diazotype material sensitized with the corresponding 2,5-dialkoxy compounds and, when polyvalent phenols such as resorcinol or phloroglucinol are used as azo-coupling components, often yield copies in azo-dyestuffs h-aving better absorption for ultra-violet radiation. In the above definition by acyl is to be understood the radical - CO-R2, in which R2 is hydrogen or an organic radical. Such an interpretation of @acyl is usual in diazotype literature. (Compare British patent specifications Nos. 615,774, 347,430 and539,031.) The saturated or un-saturated organic radicals R, according to the above definition include saturated and unsaturated aliphatic and cycloaliphatic radicals, aromatic radicals, acyl radicals, and the cyano group. The diazotype material according to the ilivention is preferably one-component diazotype material. Upon development with weakly acid phloroglucinol developers it yields copies with brown to black azo-dyestuff images and upon development with weakly -alkaline phloroglucinol developers it yields copies with somewhat lighter brown -azo-dyestuff images. In a particular embodiment of the invention one-c6mponent diazotype material which is suitable for use as a light-sensitive planographic printing plate is employed on which ;by imagewise exposure and devac@lopment with a liquid containing an azo coupling component -a hydrophobic ink-receptive image is formed. The diazotype material according to the invention may, however, also be two-component diazotype material. In such material a slowly coupling azo-component, such as 2-hydroxy-8- biguanidinonaphthalene, 2-hydroxynaphthalene-3,6- disulphonic acid or 7'-hydroxy-l',2',4,5-naphthimidazole is preferably used. The diazotype material accordin- to the invention may also be heat-developable diazotype material, e.g. material such as described in British patent specification No. 815,005 or United States Patent No. 3,284,201. The diazotype material according to the invention may have an opaque support, such as white paper or opaque linen, or a transparent support, such as tracing paper, tracing linen, cellulose-ester foil, polyester foil, transparentized paper and the like. The diazon,ium compound may be applied direct on the surface of the support-or rnay be present in a hydrophilic film layer which may or may not be attached to the support by means of one or more sub-layers. The following table lists, but is not a complete list of, diazonium cornpounds which can be used in the diazotype material according to the invention: TABLE (4-diazo-5-N-acetyl-N-methylamino-2-methoxy)phenylthioethyl ether, (4-diazo-5-N-acetyl-N-methylamino-2-n-butoxy)phenylthioethyl ether, (4-diazo-5-N-acetyl-N-methylamino-2-cyclopentoxy) phenylihioethyl ether, (4-diazo-5-N-benzoyl-N-methylamino-2-butoxy)phenylthioethyl ether, (4-diazo-5-N-acetyl-N-ethylami.no-2-methoxy)phenylthiobenzyl ether, (4-diazo-5-N-butyryl-N-ethylamino-2-methoxy)phenylthiobenzyl ether, (4-diazo-5-N-acetyl-N-metbylamino-2-(4'-chloro)phenoxy) phenylthio-(4'-methyl)phenyl ether, Oxalic bis- (N-methyl) (N-2'-diazo-4'-methoxy-5'- (4'- methyl)phenylthiophenyl) amide,
[2]3,311,475 3 TABLE-C)ontin,ued (4-diazo-5-N-ethoxycarbonyl-N-methylamino-2-methoxy) phenylthioethyl ether, (4-diazo-5-N-ethoxycarbonyl-N-methylamino-2-n-butoxy) phenylthioethyl ether, (4-diazo-5-N-ethoxycarbonyl-N-methylamino-2-methoxy) phenylthiocarboxymethyl ether, (4-diazo-5-N-ethoxycarbonyl-N-methylamino-2-methoxy) phenylthiopotassium sulphomethyl ether, (4-diazo-5-N-ethoxycarbonyl-N-methylamino-2-methoxy) phenylthio-2'-hydroxyethyl ether, (4-diazo-5-N-ethoxycarbonyl-N-methylamino-2-methoxy) phenylthio-2'-methyl-4',4'-dimethylpentyl ether, (4-diazo-5-N-ethoxycarbonyl-N-methylamino-2-methoxy) phenylthioallyl ether, (4-diazo-5-N-ethoxycarbonyl-N-methylamino-2-methoxy) phenylthiobenzyl ether, (4-diazo-5-N-ethoxycarbonyl-N-methylamino-2-methoxy) phenylthio-(4'-methyl)phenyl ether, (4-diazo-5-N-isobutoxycarbonyl-N-methylamino-2-methoxy)phenylthioethyl ether, (4-diazo-5-N-benzyloxycarbonyl-N-methylamino-2-methoxy)phenylthioethyl ether, (4-diazo-5-N-phenoxycarbonyl-N-methylamino-2-methoxy)phenylthioethyl ether, (4-diazo-5-N-isobutoxycarbonyl-N-methylamino-2-methoxy)phenylthio-(4'-methyl)phenyl ether, (4-diazo-5-N-benzyloxycarbonyl-N-methylamino-2-methoxy)phenylthio-(4'-methyl)phenyl ether, (4-diazo-5-N-phenoxycarbonyl-N-methylamino-2-methoxy)phenylthio-(4'-methyl)phenyl ether, Adipic bis- (N-methyl) (N-2'-diazo-4'- methoxy-5' -ethylthiophenyl)amide, 4@ethoxycarbonylthio-5-methoxy-2-N-ethoxycarbonyl-Nn-butylaminodiazobenzene, 4-eyanothio-5-methoxy-2-N-ethoxycarbonyl-N-methylaminodiazobenzene, (4-diazo-2-methoxy-5-N-methyl-N-2'-chloroethoxycarbonylamino)phenylthioethyl ether, (4-diazo-2-methoxy-5-N-methyl-N-2'-diethylaminoethoxycarbonylamino)phenylthioethyl ether, (4-diazo-2-methoxy-5-N-2'-hydroxyethyl-N-benzyloxycarbonylamino)phenylthioethyl ether, (4-diazo-2-benzyloxy-5-N-methyl-N-ethoxycarbonylamino)phenylthioethyl ether, (4-diazo-2-methoxy-5-N-methyl-N-ethoxycarbonylamino) phenylthio propargyl ether. (4-diazo-2-methoxy-5-N-isopropyl-N-ethoxycarbonylamino) phenylthio-p-tolyl ether, (4-diazo-2-methoxy-5-N-cyclohexyl-N-ethoxycarbonylamino)phenylthio-p-tolyl ether, (4-diazo-2-methoxy-5-N-benzyl-N-acetylamino)phenylthio-p-tolyl ether, (4-diazo-2-mcthoxy-5-N-methyl-N-ethoxycarbonylamino) phenylthionaphthyl ether, (4-diazo-2-methoxy-5-N-methyl-N-ethoxycarbonylamino) phenylthio-homo-naphthyl ether. These diazonium compounds are (preferably) applied in the form of their diazonium salts, such as diazonium cworides, sulphates, nitrates, and metal chloride double salts (e.g., diazonium chlorostannates, chlorozincates), diazonium borofluorides,:and the like. They can be applied separately in the diazotype material according to the invention or be mixed together. Naturally they can also be used in admixture with diazonium compounds of other types. However, according as such mixtures have a lower content of diazonium compound according to the foregoing formula, the diazotype material accordin.- to the invention prepared with these mixtures will present the advantages described to a smaller degree. The diazonium compounds of the foregoing formula with an etherified mereapto group in p-position and those with an acylthio group in p-position can be prepared bY 4 starting from 5-chloro-2-(alkyl, branched alkyl, cycloalkyl, aralkyl, or aryl)oxy-lnitrobenzene. 5-chloro-2-(alkyl, branched alkyl, cycloalkyl, or a ralkyl)oxy-l-nitrobenzene is obtained from p-chlorophenol by nitrating this product and then etherifying the hydroxyl group. 5-chloro-2-aryloxy-l-nitrobenzene is prepared from 2,5-dichloronitrobenzene, for which purpose this product is fused with a hydroxyaryl compound (phenol, naphthol) 10 and potassium hydroxide. 5-chloro-2-(alkyl, branched alkyl, cycloalkyl, aralkyl, or aryl)oxy-l-.nitrobenzene is reduced to 5-chloro-2(alkyl, brarched alkyl, cycloall@yl, aralkyl, Gr aryl)oxyaniline, the amino group of which is then acylated. T'he 15 product obtained is i3itrated and then de-acylated. In the 5-chloro-4-nitro-2-(alkyl, branched alkyl, cycloalkyl, aralkyl, or aryl)oxyaniline thus formed the chlorine atom is replaced by a mono(alkyl, branched alkyl, cycloalkyl, or aralkyl)amino group, and then the free amino group 20 by a cblorine atom (according to Sandmeyer). In order to obtain the diazonium compounds with an etherified mercapto group in p-position, the 5-(alkyl, branched alkyl, cycloalkyl, aralkyl, or aryl)oxy-4- chloro2-(alkyl, branched alkyl, cycloalkyl, or aralkyl)amino-l25 nitrobenzene thus formed, is converted with a mercaptan into 5-(alkyl, branched alkyl, cycloalkyl, aralkyl, or aryl) oxy-4-(substit uent)thio-2-(alkyl, branched alkyl, cycloalkyl or aralkyl)amino-l-nitrobenzene, which product is acylated, e.g., with a carbochloride or an ester of chloro30 formic acid, and reduced to 5-(alkyl, branched alkyl, cycloalkyl, aralkyl, or aryl)oxy-4-(siibstituent)thio-2-Nacyl-N-(alkyl, branched alkyl, cycloalkyl, or aralkyl) aminoaniline, from which the diazonium compound is produced in the usual way. 35 In order to obtain the diazonium compounds with an acylthio-4-group, 5-(alkyl, branched alkyl, cycloalkyl, aralkyl, or aryl)oxy-4- chloro-2-(alkyl, branched ialkyl, cycloalkyl, or aralkyl)amino-l-nitrobenzene is brought into reaction with Na2S2 and a carbochloride or an ester 40 of chloroformic acid. The 4-acylthio-5-(alkyl, branched alkyl, cycloalkyl, aralkyl, or aryl)oxy-2-N-acyl-N-(alkyl, branched alkyl, cycloalkyl, or aralkyl)amino-lnitrobenzene thus obtained is reduced to the corresponding amino compound, which is subsequently diazotized. 45 The diazonium compounds with a cyanothio-4-group are prepared from 4-(alkyl, branched alkyl, cycloalkyl, aralkyl, or aryl)oxyaniline by s-Liccessively acylating, nitrating, and de-acylating this product. 4 - (alkyl, branched alkyl, cycloalkyl, aralkyl, or aryl)oxy-2-nitro50 aniline is converted according to Sandmeyer into thecorresponding chloro-lcompound, the chlorine atom of which is subsequently replaced by an (alkyl, branched alkyl, cycloalkyl, or aralkyl)amino group. This amino group is then acylated. 55 2-N-acyl-N-(alkyl, branched alkyl, cycloalkyl, or aralkyl)amino-5-(alkyl, branched alkyl, cycloalkyl, aralkyl, or aryl)oxy-l-nitrobenzene is provided in the 4-position with a cyanothio group by bringing this product into reaction with Br2 and KCNS. 60 From the reaction product the diazonium compound is produced by reduction and diazotization. In general, the diazonium compounds with an (alkyl, branched alkyl, cycloalky), aralkyl, or aryl)thio substituent in the 4-position are preferred. They are readily 65 accessible by preparation in the manner described above in respect of compounds having an etherified mercapto group in p-position. They usually couple to yield a preferred rather dark brown azo-dyestuff ima,-e. Hence, a preferred diazotype material according to the 70 invention contains a diazonium compound according to the above -eneral formula, in which the substituent R3 represents an @alkyl, branched alkyl, cycloalkyl, aralkyl, or aryl radical. Other preferred compounds are the diazonium com@ 75 pounds accordin.- to the above -eneral formula iii ,Ahich,
[3]3,311,475 k, i6present@ a iion-tranched altyl group with at most 5 carbon atoms, preferably with fewer than 3 carbon atoms. Diazotype material sensitized with these diazonium compounds has not only hi.-her coupling - activity, but also considerably -reater light-sensitivity than diazo- 5 type rnaterial which has been sensitized with a corresponding 2,5-di-alkoxy compound. (Th;s appears, for instance, upon exposure in a photoprinting - apparatus which is equipped with a high-pressure merciiry vapour lamp. This diazotype material according to the inven- 10 tion often proves to be over one and a half times more li.-ht-sensitive than correspo@idin.- diazotype material which has been sensitized with the corresponding 2,5. di-alkoxy compound.) Amon.- the diazonium compounds according to the 15 above -eneral formula, those in which R2 represents an alkoxy, benzyloxy, or phenoxy radical are outstanding because they are more stable than the correspondin.- diazonium cornpounds in which R2 represents an alkyl, benzyl, or phenyl radical and moreover the azo-dyestuff go images formed from them are dark-er and have better water-fastness, so that with those diazopium - compounds it is possible to make a diazotype material yielding copies with a dark, often almost black, azo-dyestiiff ima.-e, which, notwithstanding the dark shade, has @-ood absOrP- 25 tion for ultra-violet radiation and shows no bleeding of the azo-dyestuff upon development. Very attractive compounds are the diazonium compounds according to the above -encral formula in which R3 represents an alkyl, branched alkyl, cycloalkyl, aralkyl, 30 or aryl radical and R4 a methyl -roup. By star-tin.- from the correspondin- 4-nitro-2,5-dimethoxyphenylthio ether, these diazonium - compounds can be prepared in a simple way and in -ood yields by heating the ether in an autoclave with a primary non@95 aromatic amine, upon which the methoxy group ortho with respect to the nitro -roup is replaced by a monosubstituted a-mino group, subsequently the amino group thus introduced is acylated, and the resulting nitro compound is theii converted into a diazonium compound in 40 the Lisual way. Moreover, the diazonium compounds accordin.- to the above definition can be applied better than the correspondin.- diazonium cornpounds in which R4 represents a higher alkyl -roup in aqueous sensitizin.- liquids, tO45 ,-ether with aromatic sulphonic acids such as the wellknown stabilizer naphthalene-1,3,6-trisulphonic acid, without precipitates bein.- formed in those liquids. In F;at Final Report 813, pages 86, 87, and 1095 benzene diazo compounds with a N-acetyl-Nmethylarnino 5 0 group in ortho position are described. Furthermore they may also carry methyl or methoxy substituents. These diazo compounds have low li.-ht-sensitivity and couple very actively, whilst forming very li.-ht-coloured yellow tO Ted azo-dyestuffs of low contrast. With these diazo 55 compotinds no diazotype material that is suitable in practice can be made. In the diazotype material according to the invention the auxiliary a,-ents commonly used (in the - diazotype .materials) can be applied, e.,a. acids, such as citric acid, 60 tartaric acid, and boric acid; stabilizers, such as benzene and naphthalene sulphonic acids, p-phenol sulphonic acid, and their water soltible salts; metal salts, such as zinc chloi-ide, magnesium chloride, nickel sulphate, and alum; substances serving to increase the developing speed, such 65 as glycerol, polyethylene glycol, and urea; surface improving substances, such as finely divided silica (colloidal or non-colloidal), aluminum oxide, barium sulphate, rice starch, etc.; binders, such as -elatin, aum arabic, cellulose ethers, starch derivatives, polyvinyl alcohol; disper70 sions of synthetic resins, such as dispersions of - cationic, non-ionic, and anionic polyvinyl acetate; substances servin.- to i-rdprove the back,@round of the copies, such as thiourea. The phloroalucinol developers which are used in the 75 one-coinponeiit diAzOtype proce8@ ofteti Vary as to theit composition and acidity. Three weakly acid phloroglucinol developers and one weakly alkaline phloroglucinol developer are described below. @These are practical formulations and are used for development in the examples following hereafter: (the words Sorbit and Tergitol being Reaistered Trademarks). Developer A is a solution of: 4 g. of phloro.-lucinol 0.1 g. of acetoacetanilide 3 ml. of Z-ethyl 1-hexanol sulphate Tergitol 0,8 (from Union Carbide & Carbon Corp., New York 17, U.S.A.) 15 g. of beet sugar 2.5 g. of benzoic acid 14 g. of sodium benzoate 135 g. of sodium formate in 1000 ml. of water. The pH of this liquid is approximately 5.8. Developer B is a solution of: 6.5 g. of phloroglucinol 4 g. of resorcinol 10 g. of thiolirea 2 g. of the sodium salt of butylnaphthalene sulphonic acid Sorbit P (from Geigy Chem. Corp., Ardsley, N.Y., U.S.A.) 14 g. of sodium formate 22 g. of sodium benzoate 49 g. of trisodium citrate (2 aq.) 1.2 g. of citric acid in 1000 ml. of water. The pH of this liquid is 6.5. Developer C is a solution of: 5 g. of phloroglucinol 1 g. of resorcinol 3 -. of dipotassium phosphate 3 ml. of Tergitol 08 52 g. of maleic anhydride 75 ml. of potassium hydroxide solution (13.5 N) in 1000 ml. of water. The pH of this liquid is 6.9. Developer D is a solution of: 30 g. of thiourea 5.4 g. of phloroglucinol 6.5 g. of resorcinol I g. of the potassium salt of hydroquinone-monosulphonic acid a. of sorbitol 15 -.-. of beet sugar 50 g. of potassium tetraborate (5 aq.) 1.5 g. of isopropyl naphthalene sulphoni@ ac,"d in 1000 ml. of water. The pH of this liquid is approximately 9.5. The following examples will serve to illustrate the invention. In these examples the following names used are registered trademarks: Vinnapas, Nalcamine, Rotafix. Example I A sheet of white base paper of wei-ht 80 -./M.2 suitable for the diazotype process is sensitized with a solution of: 17.5 g. of 4 - benzylthio - 5-methoxy-2-N-butyryl-N -ethylaminobenzene diazonium chloride, zinc chloride double salt 4 a. of tartaric acid 1.5 g. of boric acid 2.5 g. of gelatin 30 ml. of the polyvinylacetate dispersion Vinnapas H. 60 (from Wacker Chemie G.m.b.H., Munich, Germany) 1000 ml. of water and dried.
[4]7 A sheet of light-sensitive material thus obtained is referred to hereinafter as Sheet 1. Another sheet of base paper of th-@ same kind is sensitized with a similar soltition to that mentiotied above, in which, however, an equivalent quantity of 4-benzylthio5 2,5-dimethoxybenzene diazonium chloride, zinc chl@oride double salt, is used instead of 17.5 g. of 4-benzylthio-5- methoxy - 2 - N - butyryl-N-ethylaminobenzene diazonium salt. The sheet thus prepared is referred to hereinafter as 10 Sheet II. In an exposure apparatus for the diazotype process, Sheet I is exposed undefneath a transparent ink drawing until all the diazonium compound underneath the image-free portions of the drawing has just bleached out. 15 Then Sheet II is exposed underneath the same drawing in the same apparatus during an equal period of time. Both sheets are developed with the developer A described above, according to the so-called thin-layer method. Although both diazonium compounds have high 20 @coupling activity, it is clearly observable that the image on Sheet I has been developed more rapidly than that on Sheet II. The copy obtained with Sheet I shows a brown image on a clear white back,-round. The copy obtained with 25 Sheet 11 shows a black image on a foggy grey background. The diazonium compound u-qed in Sheet I is prepared as follows: 5-chloro-2-methoxyaniline is acetylated, nitrated, and 30 deacetylated. The 5 - chloro - 4-nitro-2-methoxyaniline is converted into 5-ethylamino-4-nitro-2-methoxyaniline with mono-ethylamine. This product is diazotized and then sandmeyered to 5- ethylamino-4-nitro-2,methoxy - 1 - chloro@benzene, from 35 which through reaction with benzylmercaptan the 5-etbylamino-4-nitro-2-methoxyphenylbenzylthio ether, melting at 95-97' C., is obtained. This product is converted with butyryl chloride into the 5-N-ethyl-N-b utyrylamino-4-nitro-2-methoxyphenyl-b@-nzylthio ether. The nitro group is 40 catalytically reduced and the amino group thus formed is diazotized, after which the diazonium compound is obtained in the form of the chlorozincate. Example II White base paper of weight 50 g./M.2 suitable for the 45 diazotype process, which has been transparentized with an alcoholic resin solution, is sensitized with a liqiiid containing: 50 g. of adipic bis (N-methyl) (N-2'-dia zo-4'-metboxy-5'- 50 ethylthiophenyl)amide chlorozincate 5 -. of tartaric acid 1 g. of boric acid 2.5 g. of gum arabic 30 ml. of Vinnapas H. 60 55 1000 ml. of water and dried. A sheet of the very light-sensitive diazotype paper thus prepared is exposed underneath a letter which has been typed on one side until the diazonium conipound under60 neath the white image portions of the l.-tter has largely bleached out, and is then developed with developer C according to the so-called thin-layer method. The copy thus obtained. shows a brown ima.-e on a fo.-gy light-brown background and is eminently suitable 65 f'r use as an intermediate original for makin.- further copies. The diazonium compound used in this example is prepared as follows: 5-chloro-2-methoxyaniline is acetylated and nitrated. 70 The 5-chloro-4-nitro-2-methoxy-N-acetylaniline is brought into reaction with monomethylamine after de-acetylation. In the 5 - methylamino - 4 - nitro - 2 - methoxyaniline tbus formed the free amino group is stibsequently replaced by a chlorine atom through sandmeyering. By causing the 75 3,311,475 5-methylamino-4-nitro-2-methoxy - I - chlorobenzene thus formed to react with ethylmercaptan, 4-etbylthio-2methylamino-5-methoxy-l-nitrobenzene is obtained, which is acylated with adipyl chloride to adipic bis (N-methyl) (N - 2' - nitro - 4' - methoxy - 5' - ethylthiophenyl) amide. This product melts at 190-192' C. Its nitro groups are catalytically reduced, after wliich from the diamino compound the bis-diazonium chlorozineate is obtained in the usual way. Exainple III Natural tracing paper of weight 80 @./M.2 iS sensitized with the followin,- solution: 36.5 g. of 4-(4'-methylphenyl)thio-5-methoxy-2-N-a cetylN-methylaminobenzeiie diazonium chloride, zinc chloride double salt 6 -@,. of citric acid 30 -,. o'L the potassium salt of benzene-1,3-disulphonic acid 250 ml. of ethanol (96%) 750 ml. of water and dried. A sheet of the diazotype paper thus obtained is exposedunderneath an ink drawing until the diazo compound underneath the ima,-e-free portions of the drawing has lar@- ely bleached otit. It is then developed with developer B. The copy shows a brown image on a fo,-gy light-brown background. If 4-(4'-methylphenyl)thio-2,5-dimethoxybenzene diazoniiim chloride, zinc chloride double salt, had been used in the above-mentioned liquid, the diazotype paper thus obtained would have been less light-sensitive, would have had a lower developing speed, and would have Piven copies with a blue-black azo-dyestuff image having lower absorption for ultra-v-@olet radiation. The diazonium compound -used in the above-n-ientioned sensitizing liquid is prepared as follows: 5-chloro-2-metho-,Kyaniline is acetylated and then nitrated. After de-acetylation, the 5 - chloro - 4 - nitro - 2methoxyaniline is converted w;th monomethylamine into 5- methylamino-4-nitro-2-methoxyaniline, in which product the free amino -roLip is replaced by a chlorine atom through sandmeyering. By causing the 5-methoxy4chloro-2-methylamino- I -nitrobenzene thiis formed to react with p-tolylmereaptan and then acetylating the 2-methylamino group, 5 - methoxy - 4 - p-tolylthic-2-N-m,-tbylNacetylamino-l-nitrobenzepe, melting at 154-155' C., is obtained. This nitro compound is catalytically reduced to the correspondiiig amine, which is then diazotized. The resultin- diazonium compound is obtained in the T form of the zinc chloride double salt. Exaniple IV A celltilose acetate layer of weight about 20 g./M.2, applied on natural tracing paper of wei.-ht about 80 g./m.2, is superficially hydrolysed to a depth of about 4 microns and, after r.-moval of the chemicals iised for the hydrolysis by washing with water, is sensitized with the followin.- solution: 49.5 - of 4-ethylthio-5-n-butoxy-2-N-acetyl-N-meth ylami@n'obenzene diazonium chloride zinc chloride double I salt 6 g. of tartaric acid I g. of gum arabic 250 ml. of ethanol (96%) 750 ml. of water and dried. A sheet of the diazotype paper thus obtained is exposedunder@ieath a line drawing until all the diazonium compound underneath t@he image-free portions of the drawing has bleached out. It is then developed with develorer B. The copy shows a violet-brown azo-dyestuff in-iage having good absorption for ultraviolet radiation. If the above-mentioned liquid had conta:l-ued instead of
[5]9 the 5-butoxy-2-N-acetyl-N-methylamino diazonium compound, an equivalent quantity of 4-ethylthio-2,5-di-nbutoxybenzene diazonium chloride, zinc chloride double salt, the diazotype paper thus obtained would have been less light-sensitive, would have had a lower develo-ning speed, and would have given copies with dark-blue azodyestuff ima,- es havin.- lower absorption for ultra-violet radiation. The diazonitim comround used in this example can be prepared as follows: p-Chlorophenol is nitrated, and the 4-chloro-2-nitrophenol thus obtained is butylated with n-butyl bromide to 4-chloro-2-nitrophenyl-n-btityl ether. The nitro group of this product is reduced and the amino -rotip thus formed is acetylated with acetic anhydride. The 4-chloro-2acetylaminophenyl-n-butyl ether is nitrated, de-acetylated, and then brou,-ht into reaction with monomethylamine. 5-nitro-4-methylamino-2- aminophenyl-n-butyl ether is obtained. The amino group of this product is replaced by a chlorir@e atom through diazotization and sandmeyering, af',er which the product thus formed is converted into 4ethylthio-5-n-butoxy-2-me thylamino-l-nitrobenzene with ethylmercaptan. This substance is brought into reaction with acetyl chloride, as a result of which 4-ethylthio-5butoxy-2-N-methyl-N-ac etylamino-l-nitrobenzene, meltin - at II O' C., is obtained. z@he nitro -roup of this compound is catalytically reduced and the arnino group thus formed is diazotized. The diazonium compound is obtained in the form of the chlorozineate. Example V Opaque linen of wei.-ht 150 g./M.2 suitable for the diazotype process is sensitized with a solution of: 40 g. of 4-ethylthio-5-methoxy-2-N-benzyloxycarbo,y lN-methylaminobenzene diazonium chloride, zinc chloride double salt 5 g. of tartaric acid 2 @. of boric acid 300 ml. of ethanol (96%) 700 ml. of water and dried. A sheet of the light-ensitive diazotype linen thus obtained is ima,-ewise exposed as described in Example II and developed with developer A. The copy shows a black ima.-e on a foggy grey background. If, instead of the diazonium compound mentioned, an equivalent quantity of the corresponding 4-ethylthio-2,5di-methoxybenzene diazonium salt had been used, a copy with a black ima.ac on a fog.-y grey background would also have been obtained. However, the li.-bt-sensitive material would have bad considerably lower lightsensitivity and a lower developin.- speed. The diazonium compound used accordin.- to this example is prepared as follows: 5-chloro-2-methoxyaniline is acetylated, nitrated, and deacetylated. The 5 - chloro-4- nitro-2-methoxytniline thus obtained is converted withmonomethylamine into 5- methylamino-4-nitro-2-methoxyaniline, which is then diazotized and sandmeyered to the corresponding chloro compound, from which the 5 -methylamino-4-nitro2methoxyphenylethylthio ether is prepared by converting it with ethylmereaptan. This product is converted with the benzyl ester of chloroformic acid into 4-ethylthio5methoxy - 2 - N-benzyloxycarbonyl - N - methylamin o-lnitrobenzene, meltin.- at 96-98' C. From this nitro compound the above-mentioned diazonium salt is obtained in the usual way. Example VI Paper coated with a baryta layer, for instance a sheet of paper of the quality Dryphoto mat (from Papeteries Steinbach & Cie., Malmedy, Belgiurn), is sensitized with a solution of: 3,31i,476 10 25 g. of 4-(4'-methyl)phenylthio-5-methoxy-2-N-ethoxycarbonyl-Nmethylaminobenzene diazonium chloride, zinc chloride double salt 500 ml. of ethanol (96 % 500 ml. of water and dried. A sheet of the light-sensitive diazotype material thus obtained is imagewise exposed as described in Example IV and then developed by rlibbing the image side of the 10 diazotype material with a liquid containing: 30 g. of phloroglucinol 20 ml. of sodium hydroxide solution (1 1.2 N) 980 ml. of water 15 The copy shows a brown-red image on a clear white background. The copy is then rubbed with a so-called fixin.- solution, e.g. the liqtiid Rotafix B (from Rotaprint A. G., Berlin, Germany), and then wa5hed with water. 20 The copy is now suitable for use as a planographic printing plate, and at least 1000 good offset prints can be made with it. The diazonium compound used in this example may be made as follows: 25 Chloronitrohydroquinone dimethyl ether is brought into reaction with ptolylmerca@ptan and the 4-p-tolylthio2,5-dirnethoxy-l-nitrobenzene thus formed is heated for 20 hours with monomethylamine in an autoclave at a pressure of about 5 atmospheres, as a result of which 30 the methoxy group ortho with respect to the nitro group is replaced by a monomethylamino group, which is acylated with the ethyl ester of chloroformic acid. 4-(4' mothyl)phenylthio - 5 - methoxy - 2 - N - ethoxycarbonylN-methylamino-i-nitrobenzene, melting at 123-125' C. 35 is thus obtained. The nitro group of this product is catalytically reduecd, after which the diazonium salt is obtained from the amine in the usual way. Example VII 40 White base:@paper of weight 80 g./M.2 suitable for the diazotype process is sensitized with a liquid containing: 30 0-. of 4-ethylthio-5-r@iethoxy-2-N-benzyloxycarb onylN-ethylaminobenzene diazonium cbloride, zinc chloride double salt 45 7 g. of 4-(4'-methyl)phenylthio-2,5-diethoxybenzene diazonium ebloride, zinc chloride double salt 5 g. of tartaric acid 30 ml. of Vi,- inapas H. 60 1000 ml. of water 50 and dried. A sheet of the diazotype paper thus obtained is imagewise exposed underneath a pencil drawing until the diazonium compound underneath the imagefree portions of the drawin.- has largely bleached out, and is then 55 developed with developer A. The copy thus obtained sbows a black image oi a fo.-gy grey background. If in the above sensitizing liquid, instead of 4-ethylthio - 5-methoxy-2-Nbenzyloxycarbonyl-N-methylamino60 benzene diazonium chloride, zinc chloride double salt, an equivalent quantity of the corresponding 4-ethylthio-2,5dimethoxybenzene diazonium compound had been used, tie diazotype paper thiis obtained would have been considerably less li,-htsensitive, would have had a lower de65 veloping speed, and would have given a black image on a fog.-Y blue-grey back.- round. Exarpple VIII White paper of weight 150 g./M.2, coated on one side 70 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 affixed to the paper by means of an adliesive and de-acetylated to a depth of about 4 microns to an average acetyl con75 tent, calculated as combined acetic acid, of 20% by
[6]3,311,475 w-,ight (which corresponds to an average ntimber of acyl groups at the OH-groups of 0.7), is impregnated on the de-acetylated side of the cellulose acetate layer with the followin-. solution: 37.8 g. of 4-allylthio-5-me thoxy-2-N-ethoxycarbonylNmethylaminobenzene diazonium chloride, zinc chloride double salt 5 g. of tartaric acid 20 g. of the sodium salt of nap hthalene-1,3,6-trisulphonic acid 2.5 g. of gum arabic 100 ml. of ethanol (96 % 900 ml. of water and dried. A sheet of the dried diazotype material is ima,-ewise exposed as described in Example IV and developed with developer B. The copy thus obtained sbows a brown image on a clear white background. If, in the above sensitizing liquid, an eqliivalent quantity of the corresponding 4-allythio2,5-dimethoxyb@-nzene diazonium compound had been -Lised, the diazotype material thus obtained would have been considerably less light-sensitive, would have had a lower developing speed, and would have -iven copies with black azo-dyestuff ima-,es. The diazonium compound used according to this example is prepared as follows: 5 - methylamino - 4-nitro-2-metboxy-l -chlorobenzene, prepared as described in Example 11, is brought into reaction with allylmercaptan and then acetylated with the ethyl ester of chloroformic acid. 4-allylthio-2 -Nmethylamino-5-methoxy-lnitrobenzene is thus obtained in the form of a dark red oil. From this nitro compound the diazonium salt is obtained in the usual way. Exaiiiple IX A clear cellulose acetate ffim of 150 g./M.2 with an acetyl content of about 2.5 is superficially hydrolysed to a depth of about 4 microns and, after removal of the chemicals used for the hydrolysis by wa.shing with water, is sensitized with a solution of: 51 g. of 4-hydroxyethylt hio-5-methoxy-2-N-methylNethoxycarbonylaminobenzene diazonium ebloride, zinc chloride double salt 7.5 -,. of citric acid 15 g. of the sodium salt of nap tbaler@e-1,3,6-trisulphonic acid 250 ml. of ethanol (96%) 750 ml. of water and dried. The hydrophilic light-sensitive layer obtained after drying contains about 0.5 millimol of diazonium compound per M.2 of sensitized surface. A sheet of the light-sensitive diazotype material thus obtained is imagewise exposed as described in Example IV and then developed with developer B. The copy shows a brown-red image on a crystal-clear background. The azo-dyestuff image has good absorption for ultra-violet radiation. The diazonium compound used accordin.- to this example is prepared as follows: 5 - methylamino - 4-nitro-2-me thoxy-l-chlorobenzene is brou-ht inl,o reaction with hydroxyethylmereaptan and then acylated with the ethylester of chloroformic acid. 4 - hydroxyethylthio - 2 - N-ethoxycarbonyl-N-methylamino-5- methoxy-l-nitrobenzene, melting at 174' C., is obtained. From this nitro compound the diazonium conipound is obtained in the usual way. Example X White base paper of weight 80 g./M.2 suitable for the diazotype process is sensitized with a liqtiid containing: 12 20 g. of 4 - (4' - methylphenyl)tbio-5-methoxy-2-Nisobutoxycarbonyl - N - methylaminobenzene diazonium chloride, zinc chloride double salt 5 -. of tartaric acid 22 of non-colloidal silica 1.3 of carboxymethylamylose 50 ml, of an anionic polyvinyl acetate dispersion 900 ml. of water and dried. 10 A sheet of the diazotype paper thus obtained is ima-,ewise exposed as described in Example IV and then developed with developer A. The copies thus obtained show an intensive brownblack image on a clear white background. 15 If, in the above sensitizin- solution, @an equivalent quano-2,5tity of the correspondin@ 4-(4'- methylphenyl)thi dimethoxybenzene diazonium compound had been tised, the diazotype paper thus obtained would have been considerably less light-sensitive, would have had a lower de20 veloping speed, and would have given copies witli a blueblack azo-dyestuff image. The diazonium compound used in this example is prepar,-d as follows: 5 - methoxy - 4 - (4' - methylphenyl)thio - 2 - methyl25 amino-l-nitrobenzene, prepared as described in Example 111, is @acylated with the isobutyl ester of chloroformic acid. The product tbus obtained melts at 77-79' C. It is converted into the @diazonium salt in the usual way. 30 Example XI To 100 iiil. portions of a stock solution contai-ling: 5 g. of tartaric acid 2 g. of -boric acid 35 2.5 g. of gtim arabic 10 ml. of glycerol 40 g. of rice starch 30 ml. of Vinnapas H.60 1000 ml. of water 40 is added 0.35 milli-equivalent each of the following diazonium compounds: (1) 4 - ethylthio - 5 - cyclopentoxy - 2 - N - acetyl -- Nmethylaminobenzene diazoniumchloride, zinc chloride double salt. 45 (2) 4 - p - tolylthio - 5 - p - chlorophenoxy - 2 - N - acetylN-methylaminobenzene diazonium chloride, zinc chloride double salt. (3) 4 - carboxymethylthio - 5 - methoxy - 2 - N - e tboxycarbonyl-Nmethylaminobenzene diazonitun chloride, 50 zinc chloride,double salt. (4) 4 - etbylth-lo - 5 - methoxy - 2 - N - phenoxycarbonylNmethylaminobenzene diazonium chloride, zinc chloride double salt. (5) 4 -,cyanothio - 5 - methoxy - 2 - N - ethoxycarbonyl55 N-methylaminobenzene diazonium chloride, zinc chloride double salt. (6) 4 - ethoxycarbonylthio - 5 - methoxy - 2 - N - ethoxycarbonyl-N-nbutylaminobenzene diazonium chloride, zinc chloride double salt. (7) Ethane - 1,2 - dithiol - bis - (4' - diazo - 2' - methoxy60 5' - N - ethoxycarbonyl - N - methylaminophenyl)ether, chlorozincate. With each of the seven sensitizing liquids thus prepared, sheet of white base paper for the diazotype process is 65 sensitized. The sheets are marked with the figures 1 to 7, so that the figures correspond with those of the diazonium compounds in question. The seven sheets are exposed linderneath a transparent 70 ink drawing until all the diazonium compound underneath the ima-e-free portions of the drawing has bleached out. Then each of the sheets is divided into two equal parts. One half is marked with an a and then developed with developer B; the other half is marked with a b and 75 then developed with developer D.
[7]13 All tie mat,-rials are found to be very light-sensitive and to have a very hi.-h developing speed. All the copies show a white background. The azodyestuff ima.-e of: sheet la is violet-brown:and that of sheet lb is li.-ht-,brown sheet 2a is dark-brown and that of sheet 2b is light-brown sheet 3a is brown-red and that of sheet 3b is yellowbrown ,Sheet 4a is violet-black and that of sheet 4b is brown sh,-et 5a is red and that of sheet 5b is orange-brown sheet 6a is brown and that of sheet 6b is light-brown sh-.et 7a is brown-red and that of sheet 7b is yellow-brown. Diazonitim compound No. I is prepared as follows: p-chlorophenol is converted with cyclopentyl bromide into 4-chloro-l-cyclopentoxybenzene. The product thus obtained is nitrated, after which the nitro group thus introduced is reduced and the amino group thus formed is acetylated. The 5-chloro-2-cyclopentoxy-N-acetylaniline is nitrated and then de-acetylated. The chlorine atom is su@bsequently replaced by a monomethylamino group and the free arnino group is replaced by a chlorine atom according to Sandmeyer. The 4 - chloro - 5 - cyclopentoxy - 2 - methylamino-l-nitrobenzene is brought into reaction with ethylmereaptan and then acylated with acetyl chloride. The 4 - ethylthio - 5 - cyclopentoxy - 2 - N - acetyl - N - methylamino-l-nitrobenzene m-@lts at 108-111' C. This nitro compound is converted into @the diazonium salt in the usual way. Diazonium compound No. 2 is prepared from 5-chloro2 -p-chlorophenoxyaniline, which is supplied by Rohner A.G., Pratteln, Switzerland, under the trade name FRbase. The product in question is acetylated, nitrated, and de-acetylated. The .5-chloro-4-nitro-2-pchlorophenoxyaniline is brou.-lit into reaction with monomethylamine, after which the free amino -roup is replaced by a chlorine atom accordin.- to Sandmeyer. This chlorine atom is subsequently replaced by a p-tolylthio group. Into the monomethylamino group an acetyl group is introduced with the aid of acetyl chloride. The 4-p-tolylthio-5-p-chlorophenoxy-2-Nacetyl-Nmethylamino-l-nitrobenzene melts at 161-162' C. From this n;tro compound the diazonium salt is obtained in the usual way. Diazonium compound No. 3 is prepared from 5-chloro2 -methoxyaniline. This ptoduct is acylated, nitrated, and de-acylated, and subsequently brought into reaction with manomethylamine. The 4-nitro-5-methylamino2-methoxyaniline is converted into 4-chloro-5-methoxy-2-methylamino-l-nitrobenzene according to Sandrneyer. The chlorine atom of the latter product is replaced by a carboxymethylthio -roup with the aid of thioglycolic acid, after which the monomethylamino -roup is acylated with the ethyl ester of chloroformic acid. The 4-carboxymethylthio-5-methc)xy-2 - N - ethoxyca rbonyl-N-methylamino-lnitrobenzene, melting at 172174' C., is converted iiito the diazonium salt in the usual way. Diazc).-iium com@pound No. 4 is prepared from 4-chl oro5-methoxy-2-methyla@minol-nitroberizene (see the preceding preparation). This product is brought into reaction with ethylmereaptan and then acylated with the phenyl ester of chloroformic acid. The 4-ethylthio-5metho,xy-2-N-phenoxycarbonyl-N-mothylar@iino-1 - nitrobenzene melts at 131-133' C. It is converted into the diazonium salt in the usual wav, Diazonium compound No. 5 is prepared from p-anisidine, which for this purpose is acylated, nitrated, and deacylated. The a-mino -roup of the 4-methoxy-2-nitroaniline is replaced according to Sandmeyer by a chlorine atom, which is subsequently rel,)Iaced by a monomethylamino aroup. The 5-methoxy2-methylamino-l-nitrobenzene is acylated with the ethyl ester of chloroformic acid, after which the product of the acylation is brought into reaction with bromine and potassium rho,danide. The nitro .- roup of the 4-eyanothio-5-methoxy-2-N-eth0,311,475 . 14 oxycarbonyl-N-methylamino-l-nitrobenzene is reduced, and the amine tbus forined, which melts at 142' C., is diazotized. The diazonium compound is obtained in the form of the chlorozincate. Diazonium compound No. 6 is prepared from 5-chlor o2-metboxyaniline. TWs product is acylated, nitrated, deacylated, and then brought into reaction with mononbutylamine. The 4-nitro-5-n-butylamino - 2 - methoxyaniline is conver-ted according to Sandmeyer into 4-chloro10 7-n-butylamino-5-methoxy-l-nitrobenzene, which is subsequently converted by means of Na2S2 and sulphur into 4-NaS-2-n-butylamino-5-methoxy-I - nitrobenzene, wbich melts at 130-132' C. This product is acylated with the ethyl ester of chloroformic acid. The 4-ethoxycarbonyl15 thio-2-N-n-butyl-N-ethoxycarbonylamino-5-methoxy - 1nitrobenzene is a redbrown oil. Fi-om the nitro co-mpound the diazonium salt is obtained in the usual way. Diazonium compound No. 7 is prepared from 4-chloro5-methoxy-2- methylamino-l-nitrobenzene (see: prepara20 tion of diazo com@polind No. 3). This product is converted with ethane-1,2-dithiol and then acylated with the cthyl ester of chloroformic acid. Ethane-dithiol-bis(4'-nitro-5'-N - ethoxycar-bonyt - Nmethylamino-2-m.- thoxyphenyl)ether is obtained, which 25 inelts at 175' C. and from which the bis (diazonium chlorozincate) is obtained in theusual way. E.Tample XII Wh;tc base paper of weight 80 g./M.2 suitable for th-- 30 diazo type process which has been precoated with an aqueous dispersion of silica and then dried, is sensitized with a liquid containing: 8 g. of 4-ethylthio-5-methoxy-2-N-methyl-N-acetylamino35 benzene diazonium chloride, zinc chloride double salt 8 g. of tartaric acid 4,g. of boric acid 600 ml. of Vinnapas H.60 400 ml. of water 40 and dried. On tic light-sensitive layer an intermediate layer is for med by applyin.@ a solution of: 100 g. of the polyvinyl acetate Vinnapas U.W.50@ in 1000 45 ml. of trichloroethene and drying. O@ l the intermediate layer a top layer is formed with the aid of a liquid containing: 50 5 g. of 2,3-dihydroxynaphtbalene 20 -. of non-colloidal silica 46 g. of N-acyl-N'-2-hydroxyethylethylenediamine Naleami ne A12 (from Nalco Chemical Co., Chicago 38, 55 Ill., U.S.A.) 100 0 ml. of petroleum ether. The dried light-sensitive material is ima,-ewise exposed und erneath @a transparent India ink drawing until the di60 azonium compound underneath the ima,@e-free portions of the drawing has bleached otit, and is then developed by gliiding it over a heated roller having a temperature of about 140' C., the back of the sheet contacting the roller surface. 65 The copy shows ared image on a white back.-round. The diazonium compound used in this example is prepared as follows: 5-methylamino-4-nitro-2-methoxy-l-chlorobenzene (see Example 11) is broii.-ht into reaction with ethylmereaptan. 70 The reaction product is acetylated. The 5,metho xv-4ethylthio-2-N-acetyl-Nmethylamino-1 - nitrobenzene thus obtained melts at 162-164' C. This nitro compound is reduced to the corresponding amino compound, which is then diazotized. The resulting diazon;um compound is 75 obtained in the form of the zinc chloride double salt.
[8]@,311,475 15 Exainple XIII White base paper of weicht 80 g./M.2 suitable for the diazo-type process is sensitized with a liquid containing: 16 g. of 4-ethylthio-5-metboxy-2-N-methyl - N - ethoxy5 carbonylaminobeiizene diazonium chloride zinc chloride double salt 20 of tartaric acid 5 g' of boric acid 20 g. of the sodium salt of naphthalcne-1,3,6- trisulphonic 10 acid 2.5 g. of gm. arabic 15 g. of 7'-bydroxy-l',2',4,5-napbthimidazole 30 ml. of Vinnapas H.60 1000 ml. of water 15 and dried. A sheet of the two-component diazotype paper thus obtained is imagewise exposed as described in Example 11 and then developed in amimonia vapour. The copy shows a red image on a f oggy red back20 ground. If, in the above sensitizing liquid, an equivalent quantity of the corresponding 2,5-dimethoxy compound had been used, the diazotype paper thus obtained would have been much less light-sensitive and would have had a 25 lower developing speed. The diazonium compound used in this example can be prepared as follows: 4-ethylthio-2,5-dimethoxy-l-nitrobanzente (prepared for instance, as described in Dutch patent specification No. 30 51,536) is heated for 20 hours with -monomethylamine in ,an autoclave at a pressure of about 5 atmospheres. The reaction product is acylated with the ethyl ester of chloroformic acid, after which from the 4 -ethylthio-5- methoxy-2-N-methyl-N-ethoxyc-arbonylamino - 1 - n@itro35 benzene thus formed, the diazoniurn compound is - obtained in the usual way. What we
