Chemicals and Materials for Collotype.
GELATINE.—The basis of the Collotype process is gelatine—the finest purified animal glue—and the important part it plays in the process demands an acquaintance with its properties, which are found to differ widely, according to its origin and method of preparation. Gelatine suitable for Collotype should be free from all impurities—particularly alum, which is not infrequently added in small quantities during manufacture. Dr. Eder, in particular, has made most minute examinations of various samples, more especially with regard to their suitability for Collotype, Carbon, and the Galvanographic processes, and his opinion, agreeing with that of other experimentalists, is here quoted:—
The two principal modifications of gelatine are those produced from bones, sinews and skins of animals, and from the air bladder of the sturgeon, the latter variety, better known under the name of isinglass, represents, from a chemical point of view, glue in the purest form. On account of its high price and ever-varying quality as found in commerce, it must in practice give place to a glue or size containing chondrin, and prepared from bone and gristle. Another objection is, that plates prepared with an admixture of isinglass are less durable than those containing gelatine only. On the other hand, it certainly possesses advantages of its own, which will be more fully considered hereafter. A gelatine suitable for collotype must absorb plenty of water and swell out, but not liquefy after having been soaked in cold water for twenty-four hours. Gelatine or isinglass prepared from the bladder will not stand this test, but, on the contrary, partially disintegrate. The consistency and bearing capacity of a jelly formed by dissolving gelatine in water by means of heat and allowing it to cool, form, in the opinion of Lipowitz, a safe and reliable means of forming a judgment as to its suitability for collotype. Dissolve by first soaking five grammes in 45 cm. of distilled water for several hours, afterwards apply heat, and allow to stand twelve hours to set. For purposes of comparison this should always be done in a glass of the same diameter. A small tin or zinc slip is placed across the top of the glass vessel containing the jelly; through the centre of the tin a hole is pierced, through which a wire moves easily up and down. To its bottom end is soldered a piece of tin, of about 15 cm. diameter, the convex side lying upon the surface of the gelatine. On the other or upper end a small funnel is placed, large enough to contain 1-1/2 kilo. of small shot. The weight of the wire and funnel being ascertained, it will be a simple matter, by also weighing the shot, to calculate the weight required to sink the instrument into the jelly, and to ascertain with accuracy its weight-bearing capacity and proof of the relative value of various samples for Collotype printing. If otherwise suitable, the variety capable of supporting the greatest weight before yielding will be the one to select. The power of absorption of different samples varies considerably; for example, the Collotype gelatine of Creutz absorbs in two hours 30 parts of cold water poured over it. Nelson’s patent opaque, in the meantime, only absorbs five parts, but after a further period of 4-1/2 hours the difference is equalised, as it will absorb 25 parts more of water, making altogether exactly 30 parts. This experiment proves the latter to be a harder quality than that of Creutz, and it necessarily requires a somewhat different treatment for the production of the best results.
Isinglass or fish glue, although, as before stated, a finer quality of glutin than the ordinary gelatine of commerce, is, on account of its high price and varying quality, comparatively little used. The addition of this substance also softens the gelatine layer. On the other hand, it possesses certain properties which render its use at times desirable; for instance, it does not dry so completely as gelatine, the layer prepared with it consequently gives cleaner and more even proofs, a point particularly noticeable in the earlier impressions. Such prints will also exhibit greater brilliancy, and this is of especial consequence in work produced from photographs from nature, in which class of work the half-tones are too often wanting. Some operators take even equal parts of isinglass and gelatine, but such layers must be very thin, and dried quickly. Thick layers are liable to crack or fly, and in use to refuse to take the ink, which must for such film be used in greater quantity and thinner than when gelatine alone is employed. A solution of isinglass is not so readily prepared as one of gelatine. It is necessary to allow it to soak in cold water for from twelve to twenty hours, and the temperature then gradually raised to nearly boiling point, at which heat it should be maintained for some time longer, and then filtered through flannel into the gelatine solution. In printing from these plates, particularly when the proportion of isinglass exceeds one-third the amount of gelatine, there is a disagreeable tendency of the printing paper to adhere in the high lights—that is, in those parts of the print layer which are represented in the negative by entire opacity—as in the sky of a landscape or a background which has been “stopped out” on the negative. On other portions of the plate where the light has more fully acted—during the printing in the printing frame—this troublesome defect will not be observed. The fault is more noticeable when the dull enamel paper is used, while a hard, well-sized letter paper presents the other extreme. Further details of printing papers will be found in another chapter.
In the introductory chapter of this work the photo-chemical qualifications of the bichromates of ammonium and potassium with regard to collotype are considered.
Bichromate of Potassium is found in the well-known rich orange-red crystals. It is readily soluble in cold water (1.10). It may be easily recrystallised and purified readily out of either a hot, warm, or cold solution, and forms in thin layers of fine crystals. Therefore, in using it for collotype, care is needed not to exceed the strictly necessary proportion, as the plate may be hopelessly spoiled by the partial crystallisation of the salt, which will probably show during the process of drying. The maximum addition of bichromate of potassium in proportion to the weight of the gelatine may differ according to the peculiarities of the latter. Dr. Eder considers about 3/10 to 4/10 by weight of this salt in a dry state may be added to a gelatine, which will absorb from six to ten times its weight of water, without fear of crystallisation. There are, however, many gelatines that are incapable of working with more than 2/10. Rapid drying of the plate in a current of air, and at a temperature of 40° C., will, to some extent, obviate this objectionable feature. By reason of its comparative insensitiveness to light and this facility of crystallisation, and notwithstanding its comparative low price, it is now far less used in collotype than
Bichromate of ammonium, the crystals of which somewhat resemble those of the potassium salt. In colour they are of a browner hue, and readily distinguishable, since when heated on platinum deflagrates, emitting sparks and leaving a residuum of very finely-divided oxide of chromium. The ammonium salt does not, however, so readily crystallise on account of its considerably greater solubility in water compared with bichromate of potassium. By comparison, 12 parts of the ammonium salt are equal to 15 parts of that of potassium. At least 1/3 to 1/4 more of the former may be used without disadvantage or fear of it crystallising out; it will, on the contrary, improve the quality of the film or layer. The ammonium salt will also be found comparatively more soluble in hot water, but care must be exercised that the solution never reaches the boiling point, neither should the heat of the drying box ever exceed 50° to 60° C., or the films will present a pale brown appearance, and will prove alike insensitive and partially insoluble. The single and tri-salts, offering no advantages over those already described, may be dismissed without further consideration. It may be remarked for non-chemists that the addition of any acid to the chromated gelatine solutions inclines to the formation of trichromates of the alkalis; and, on the contrary, the addition of free ammonia, or any other free alkali, produces simple chromates. The addition of ammonia to the chromated solution has been strongly advocated in many quarters, but as the result of numerous experiments, it may be definitely stated that the supposed advantages are more than counter-balanced by the numerous disadvantages arising from such addition. The mixing, in equal or other proportions, of the potassium and ammonium salts has been recommended, but there is no real gain or sufficient reason for preferring any of these combinations to the ammonium salt alone. Besides the chromates of the alkalis, several other salts as well as acids are used in Collotype printing, although seldom, and then only in small quantities and for special purposes, such, for instance, as hardening the print layer, or for the purpose of facilitating the retention of moisture in the film. For the former purpose small quantities of chrome alum are sometimes added; while for the latter chloride of sodium or chloride of calcium are sometimes added to the chromated gelatine solution at the time of coating the plates, or are added as ingredients to the so-called etching or damping solution which is frequently applied to the plates during the printing. Glycerine answers for this purpose, and is to be preferred. It should be borne in mind that all additions to the film to facilitate its retention of moisture lessen its adhesiveness to its support. And with regard to the direct addition of the substances mentioned to the film during the preparation of the plates, it is not very apparent how such readily-soluble matters can remain in the film after the prolonged and careful washing the plates should be subjected to after exposure in the printing frame. On these grounds the addition of such substances to the damping solution is more rational and certainly more effective.
Alum and Chrome-Alum causes the gelatine to set sooner without precipitation, and harden the layer considerably after drying, and although gelatine, as well as glue, always contains more or less chondrin, which is precipitated by alum, great care is necessary in the addition of the latter; and it is better that such addition should be made immediately before the hot solution be poured upon the plates, otherwise a precipitation will ensue, which, although very finely divided and at first scarcely visible, will become more apparent during the drying of the plates, and finally show in the picture in innumerable white spots.
Silicate of Soda is almost indispensable as a substratum in the preparation of collotype plates, although many practical workers still adhere to the method originally proposed and practised by J. Albert, of Munich, who used as a substratum a chromated solution of gelatine and albumen, rendered either partially or wholly insoluble by exposure to light. The silicate is here considered as having about the consistency of syrup. If more fluid the adhesive power of the substratum will not realise expectations, and the plates will require very careful handling if even a few hundred impressions are required.
The composition of the film, the exposure of the plate through the back, and the careful treatment of the layer in the actual printing operations are all matters which considerably affect the “life” of the plate, and to which we shall again return.
Chloride of Zinc is used for hardening special parts of the collotype plate, and is easily prepared by dissolving—to saturation—sheet zinc in hydrochloric acid, filtering, and reducing as circumstances may demand.
Tannin and Tannic Acid in strong solution harden the film, and may be applied to certain parts to cause it to “take” the ink. For instance, to remove, or rather harden, spots which refuse the ink and consequently show upon a dark ground; and also to write names or titles to the plates. Written additions of this character must, of course, be reversed, as in lithography. The addition of tannin to the chromated gelatine before coating the plate is recommended by Waterhouse, he considering such addition confers greater lasting power to the films so treated.
Cyanide of Potassium and Ammonia.—All alkalis or carbonates of the alkalis have a directly opposite effect upon the printed layer to that last referred to. By the judicious use of one or the other of these agents spots printing light or dark may be either removed or considerably modified.
Glycerine and Sugar and similar easily soluble organic substances, added to the chromated gelatine, would assist the easier and evener damping of the plate, but render it more susceptible to damage, and the desired effect is better attained by suitable additions to the damping water.
Organic Acids.—Citric acid and tartaric acid are recommended as additions to the chromated gelatine, partially as influencing the so-called “grain,” and also as additions to the damping solution to facilitate the production of cleaner prints. Experience with these substances shows that the print layer suffers from their use, and for clearing up a plate inclined to yield dirty impressions a weak solution of ammonia is far preferable.
Nitric Acid has even been recommended for occasionally damping the plate in certain cases, after which the most delicate half-tones should be reproducible. An experienced collotypist ought never to be under the necessity of adopting such desperate remedies, which more often than not rapidly and entirely spoil the plate, and it is better to at once prepare a new one.
Ox Gall remains to be mentioned as exercising a beneficial influence upon the print layer under certain circumstances. It considerably hardens the gelatine, and tends to reduce the annoying tendency of the film to adhere to the paper in the high lights. Ox gall was first used at the Royal Printing Works in the “glass” printing process there utilised for the reproduction of line subjects. Some operators of eminence consider that in collotype its use should be strictly confined to lineal representations, as by its continued use the half-tones are partially lost.
Ink and Paper.
Of great importance is the careful selection of the materials for the printing proper—i.e., the printing inks and papers, and the sometimes necessary admixtures of the former.
Printing Ink.—The most simple and suitable of all greasy or oily printing ink is the best chalk ink, as used in lithography. It is composed of finest lamp black thoroughly incorporated with boiled linseed oil (varnish). The collotypist must, in addition to different coloured ink for mixing with the black, be provided with thin boiled oil (middle varnish), and also turpentine and olive oil, the latter being used to thin or reduce the printing inks, which, as usually supplied to the trade, are too stiff for immediate use. When in printing it is necessary or intended to use an admixture of several colours, they must be first well ground in turpentine and the latter allowed to evaporate. A small addition to the chalk ink of indigo or Prussian blue greatly improves its colour and printing power, but may be considered more suitable for the reproduction of line or stipple subjects. A dash of Venetian red or carmine imparts to the chalk ink a warmer tone, resembling the colour of an ordinary silver print. Whoever ventures on colour printing must be able to prepare all the necessary combinations with the greatest exactness, and should use for each a special inking slab and roller. In the chapter dealing with the printing, further particulars will be given as to the mixing and thinning of the colours. The Quality of Paper suitable for collotype may be next considered. Without doubt the best is that known as dull enamel, or chalk paper, which is now supplied of a pink tone as well as of the ordinary white quality. It should not be glossy or adhere too strongly to the printing surface, as the enamel will, under such circumstances, be partially or wholly torn from the paper, a difficulty equally observable whether the paper be used damp or dry. As previously observed, the adhesive power of the printing surface increases with the softness of the same. This may arise from using a small percentage of bichromate or a short exposure to light, in which cases it is always more apparent in such parts, as the densest portion of the negative may have been entirely protected during the copying in the printing frame, or it may arise from the addition of too great a proportion of isinglass. On the other hand, a gelatine film strongly chromated, proportionately longer exposed, and in which there is no isinglass, will be less likely to exhibit this annoying tendency.
Well-sized fine glazed papers generally adhere least, and are usually laid on dry. When the impressions are to be issued without glaze very thin fine-surfaced cardboard—not enamelled—is frequently used, and the margin of the printing plate covered with a suitable mask. Any well-sized paper possessing a fine surface may be used. Impressions on such paper may be passed through a weak solution of gelatine, and after drying, rolled, varnished, mounted and again rolled. Any retouching must be done immediately after the sizing, and before the application of the varnish. Enamelled papers require a special glaze, not a lacquer, or are finished without glaze at all.
