DE2038312A1 - Photographic material - Google Patents

Description

PAT E H TA NV / Ä LTf

-DR ₁ -ING. BY KREISLER DR.-ING. SCHÖNWALD 2038312 DR.-ING. TH.-M-EYEILJlR. FUES DIPL-CHEMv ALEK FROM KREISlER DIPL-CHEM. CAROLA KELLER DR.-fNG. KLGPSCH

COLOGNE T ₄ DEICHMANNHAUS £ 5χ _η

Mr / Breu

EI du Pont de liemours & Company, Wilmington 19 S9S, Delaware, United States from Amex ^% ika

Photographic material

The invention relates to photographic materials insbescn- 'Λ particular those which are suitable for the production of lithographic printing plates.

It is known to use lithographic plates of gelatin silver halide emulsion layers divide out. According to a related process, an exposed layer is made from a G-elatine silver halide emulsion with a tanning developer treated, which converts the gelatin in the imaged areas into an oleophilic colloid. That developed Gelatin silver image can also be used for making a lithographic Plate to be used. You can do the silver picture use to prevent the oxidative degradation of gelatine in the image * areas to catalyze and in this way an oleophi- ™ Ie lower layer to expose.

In the well-known bromine-oil printing process, the gelatine-silver image bit treated in a bleach bath that dis gelatin tanned in the imaged areas, making them suitable for printing inks becomes receptive. Each known method can produce a silver image free of associated silver halide including a gelatin silver image can be converted into a lithographic image by successively Carries out the following procedural steps: First treated one the picture with a bleaching bath, which the silver picture in a picture from Sclrwormetall- and / or silver connections transfers and then sets these connections

'10S84S / 1Sfl2

an alkaline solution you only slightly soluble organic compounds that "contain SkI ₁ -SeH, -OH or -BH-öruppen" to form compounds that are less soluble than the starting products of the oxidation and the illustrated areas of the plate are oleophilic do.

The procedural texts corresponding to the state of the art go τοπ a normal silver picture or a gelatin silver ^ image out, -that by common photographic methods a photosensitive containing gelatin silver halide Layer was obtained.

These methods have several disadvantages. You are re their applicability is limited, as they have a lot of experience require complex saturation, run slowly and thereby require fixing and washing stages «also own the plates obtained as printing plates only take part in a course Lifespan"

The invention is based gave up, deliver zn photographic materials which can be processed quickly and with conventional methods for lithographic printing plates, which are made in a very short time ready for printing ■ can and have a relatively long life as printing plates. . - - -

The invention is based on a photographic material consisting of a layer support with an overlying water-permeable protein-containing. Layer of one colloidal silver halide emulsion,. as one of one with the surface of the emulsion layer Kexacyancf errat existing situation effectively assosiier-t is j which errat a heavy metal hexacyanoferrate (II) or a heavy metal heiracyanoferrate ClII) contains .;

* "3 - OWÖIMAL

Lithographic printing plates can then be made by imagewise. Exposure of a photographic material containing a silver halide emulsion layer to actinic radiation, development of the latent silver halide component present in the emulsion layer, treatment of the developed layer as an aqueous solution containing copper (H) ions, Tim to convert the developed silver image into silver ions, whereby-the werden- made "exposed areas of the emulsion layer for oily ink receptive. This leads according to the invention important that in operative association with the surface of the emulsion layer one, layer of hexa- ä ferrocyanide is present, a Schwemmet all assembling Hexacyanof errat- (II) or Hexacyanof errat- (III). A photographic developer substance has expediently been incorporated into the emulsion

The emulsion layer of gelatin SIX foerhalide can contain silver chi or id ^ silver chlorobromide * as well as silver bromide or silver iodobromide crystals, which are present dispersed in a gelatin binder, which according to one embodiment of the invention on a support with formation of a layer weight of binding ens I rag SiI berhalogenid / dm was applied. The flenge of Silberhai applied ogenids depends somewhat on the mashed ™ results, but at least one must mg / dm exist to provide a lithographic image. There is no upper limit for usable layered food per se, but there is no advantage in using more than 100 mg /

2 ·

cm silver halide to be used. Impeccable results If layer weights are set i ^ on about 5

50 mg / dm silver halide obtained
be chromatically sensitized.

50 mg / dm silver halide obtained. The emulsion can pan

Preferably one overcoats the emulsion with one thin abrasion protection layer made of gelatine or el

10984B / 1B92

water-permeable protein-containing colloids, "the iniidazole groups contain. The abrasion protection layer can then According to one embodiment of the invention, the. Hexacyanoferratsol included, but it has proven to be particularly useful the hexacyanoferrate last either above the emulsion or to apply the abrasion protection layer, if any. Suitable protein-containing colloids, .that Instead of or in addition to gelatin, gasein and zein are used.

The hexacyanoferrate sol comprises an aqueous dispersion of Hexacyanoferrate ions (H) (errocyanide) or eexacyanoferrate ions (III) (Eerricyanid) with a suitable Heavy metal cation. Preferred cations are copper (II), Hickel (II), cobalt (II), palladium (II) and shodium (II). The one used to coat the gelatin-silver halide emulsion angex '/ andte Hexacyanof erratsol contains 0.005 "to 0.1 moles of hexacyanoferrate in liters. Coating aids can be added to the sol such as complex-forming substances, for example Nitrate ions, added four. The latter serve to control the concentration of free cation to provide optimal results.

In the photosensitive layer, there should be sufficient Amount of hardeners present, either of the emulsion and / or the abrasion protection layer and / or the hexacyanoferrate sol added so that no significant amounts of colloid are transferred during pressing.

As a support for the emulsion layer of the invention Films made from macromolecular organic polymers can be used. Examples: cellulose derivatives such as cellulose acetate, Cellulose triacetate or cellulose mixed esters; ■ Polymerized vinyl compounds are also suitable, for example Hisc »/ polymers of vinyl acetate and vinyl chloride, also polystyrene and polymerized acrylates.

1O'904S / 1 592 "" W " ³ '^

'A carrier film made from the polyester ε-product has proven itself Diarboxylic acid with a polyhydric alcohol. . according to the specifications of the USA patent. 2 779 -6S «·." and the patent specifications listed in the associated description has been. Other hydrophobic "" '..'. Films are: The poly-ethyl-enterephthalate / isophthalates according to British Patent 766 290 and the Eeanadic Patent 562,672-as well as those films produced by condensation of terephthalic acid and dimethylphthalate with; Propylene glycol, " Diethylene glycol, tetramethylene glycol or cyclohexane-1,4-dimethanol ~ (hexahydro-p ~: xylene alcohol) received .. '', films according to the ™ are also eligible U.S. Patent 3,052,54-3. The listed polyester films are particularly suitable because of their dimensional accuracy. Paper, especially paper coated with polyethylene, as well as metals can also be used for the substrate.

In keeping with the practice of the invention, the material Imagewise exposed to actinic radiation, with the help of a common developer for heavily present silver, Halide images developed into a silver image - and then containing at least 0.01 mol of copper (II) ions per liter Solution activated. The silver image can be completely converted into silver ion, but the 'activation. ™ preferably only continued until a part, - '., however' " not all of the superficially developed silver with simultaneous formation of copper (I) ion in silver ion is convicted. The activator preferably contains a copper (II) halide which converts the developed silver back into silver halide. .

After this treatment, the exposed areas are the Gelatin layers absorbent for oily printing inks and the plate can be placed directly in a printing press,.

In another use of the hatch of the invention one uses the light-sensitive, with Hexaeyanöferrat coated material or a light-sensitive silicon-berhalide-free Coating of the Hezacyanoferratsol or in one lying on a layer support, in a suitable one Form hardened, hydrophilic, water-permeable, gelatin or protein-containing layer that contains imidazo groups as a receiving material for a transfer process. In such a way of working "vrirrl a common silver image in contact with a receiving material -activated. On the silver-free receiving material a printing ink-receptive image is formed and after the receiving material has been separated off. diesel use as a lithographic printing plate.

The activator solutions used to carry out the invention are required, consist of the following substances:

1. ) Copper (II) ion in a concentration of at least 0.01 molar, preferably "at least 0.03 molar,

2.) a halogen dione which is capable of forming a silver salt, which is at most as soluble as silver chloride, and which, when added, has a concentration of 0.01 molar to about 0.5 molar, preferably O ₁ OI until. O ₁ I molar, to deliver, and

3.) expediently iron (III) ion in such a concentration » that the ratio of concentration - "- at Copper — CII) ion to iron (III) ion. avfischen 1/5 and is about 100/1, preferably between 1/3 and -30/1, The pH value of the activator solution should be between 0.5 and 6, preferably between 1 "itrtd 3j-

The Aktivafeo-rlösiing can contain other aids, which improve the quality of the lithographic! 'latte.

0'S348 / 15§2 «B ORWiINAL

Cyanoguanidine, 1,2,3-triphenylguanidine, benzotriazole and 1,10-phenanthroline are useful auxiliaries that can be added to the activator solution. Activator solutions containing Qj ano-guanidine and 1,2y3-triphenylguanidine produce plates which start printing much faster in the press than solutions which do not contain these substances. Activator solutions containing bensotriazole provide improved plates which are characterized by a longer service life. The activation rate of the solution can be regulated by adding 1,10-phenanthroline, which slows down the activation reaction. · ™

The material of the invention lends itself well to manufacture lithographic plates directly from automatic collotype printing devices. Han can also contact or perform eeflex exposures in order to produce plates for fast f create simple document duplication.

The following examples illustrate the invention. ■ "■ ■

example 1

An Ivickel- (II) -hexacyanoferrat- (II) -Eol vairde as follows Jj

manufactured:

Solution a

0.1 molar potassium nitrate solution 10 ml

0.1 molar nickel (II) nitrate solution 5 ml

Solution; B.

0.1 molar Kalj-uciliexacyanoferrat- (ll) -

solution 15 ml

Saponin (10 % aqueous solution) 1 ml

Thymol (5 g / 100 nl of ethanol) 2 tu

Water '82 ml

1 NC ^f 5 S 4 S / 1 δ 9 2

- δ - ■

A solution vmrde of the solution B added over -15 seconds with vigorous Hühren at 24 ⁰ C.

_R to a coated with an adhesive layer base film of polyethylene terephthalate, which had been prepared according to Example 4 of the US Patent 2,779,684, vmrde an ortho-sensitized gelatin silver chlorobromide emulsion applied at 70 mol .-% Broraid 30 mol. - % Chloride and which contained 111 g gelatin per half of silver halide; the layer was applied with a layer weight of 88 nm / dn of silver halide mg / dm gelatin which had been hardened with 4.25 · S dimethylolurea per 100 g gelatin. The material was then coated with Hickel- (II) -hexacyanoferrate ~ (II) -sol in a red safety light, at a speed of 2 , 44 m / min, and a temperature of 24 ° C and then dried with hot air.

A sample of the material was passed through a halftone and line test negative for 6 seconds with a 500 Vatt HSP-2 reflector spot ("reflector photospot") - ViolframfaderLampe exposed, held at a distance of 127 cm vrurde ura worked at a voltage of 15 volts. The exposed sample was treated for 20 seconds at 22 ° C. in a conventional hydroquinone / 1-phenyl-3-pyrazolidone developer developed of high pH, containing 0.25 g benzotriazole per liter; it was then rinsed with water for 5 seconds and then

without further fixing 30 Ssk. at 22 ° in an aqueous Bath activated with the following composition:

3-molar copper (II) nitration solution 3-Biolar citric acid solution
3 molar potassium bromide solution
1 molar iron (IIl) nitrate solution ■ '■ *' ■ "■ - ■" - remainder: add water

50 ml 50 ml 5 ml 15th HiI 1000 ml BATH ORIGINAL

The activated sample was rinsed for 5 seconds, placed in an office machine for offset copying, and with an as after The moisturizing solution produced is rubbed in as indicated standing.

First, a concentrate of the moistening solution was made from with the following composition:

3 molar aqueous orthophosphoric acid solution IC ml

0.5 molar aqueous solution of trisodium phosphate 25 eI

Remainder: add water to 1000 ml

The moistening solution was then made on the basis of this concentrate prepared with the following composition:

Concentrate of. Moisturizing solution 20 ml

Gum ar abicum solution (1 part by weight of 100

Parts by volume of water) 20 al

Diethylene glycol monobutyl ether. 50 ml

Hest: 1000 ml of water

The plate was then inked with lithographic ink and used to print 10,000 offset copies on white hard paper. The record started very quickly with the print, all prints were of good quality.

Example 2

As in Example 1, a sample was prepared using a cobalt (II) hexacyanoferrate (II) sol instead of the nickel (II) hexacyanoferrate (II) sol. The sol was prepared as indicated in Example 1, using cobalt (II) nitrate instead of nickel (IT) -: ritrate. The sample was exposed as described in Example 1, activated, colored with ink and used for printing, whereby good copies were obtained on hard paper. \

10884B71892

- ίο -

Example 5

A sample was produced according to Example 1, viobei Copper (II) hexacyanoferrate (II) sol according to the Details of Example 1 prepared i-iurde by Eupfer- (II) -nitrafc instead of nickel (II) nitrate converted »The hexacyanof errat sol produced was used as a coating for the Gelatin silver halide layer related. Became the rehearsal exposed, activated, colored and used for printing as described in Example 1, negative offset copies were made obtain.

Example 4-

A sample was prepared according to Example 1 "using the following hexaeyanoferratsol instead of the one described in Example 1 ,

Solution a

Water 75 ml

Gum arabic (1 g / 100 ml water) 10 ml 0.1 molar x- / aqueous nickel (II) ■ —ni—

Stepped hexahydrate solution 5 ml

Polyacrylic acid (5 ml / 100 ml water) 10 ml

Solution b

Water 70 ml

Gum arabic (1 g / lOO ml water) 10 ml 0.1 molar Ealiumhexacyanoferiat- (II) -

solution 10 ml

Polyacrylic acid (5 ml / 100 ml water) 10 ml

Solution A was added to solution B over a period of 5 seconds with vigorous stirring.

After exposure, activation, coloring and printing accordingly Example 1 vjwere negative offset copies received »

'10984 8/16 92 bad original

Example 5

25th ml 5Q ml 100 ElI ICO ml 1000 ■ El

Example 4 was repeated with the exception that the AIcSi · Fourth solution had the following composition:

3 molar Eupfer (II) nitrate trihydrate solution (aqueous)

3 molar aqueous potassium bromide solution 1 molar aqueous potassium acetate solution

1 iaolar aqueous iron (III) nitrate nonahydr atsolution

Rest: water too

After coloring and printing as indicated in Example 1 good negative offset copies were obtained that were free from There was foam in the unexposed areas.

Example 6

A nickel (III) hexacyanoferrate (III) sol was prepared following the procedure of Example 4, except that potassium hexacyanoferrate (III) was used instead of KaliTHahexacyanoferrat s- (II). Analogously to the information for Example 1, a photographic Ilaterlal was produced and exposed through a 2-step wedge using a Ko. 2-2Hj-S ¹ Ot ^ UtIiClItIaEiPe, the at; ^; 5 volts and a distance of 0.61 m worked. The exposed material was placed in a l-phenyl-3-pyrazolidone / hydroquinone ENTV / iekler entiiickelt of high pH containing 0.25 Bensotriazol Z ^ e liter, after which 30 sec. In 2 / ai ^ he treated acetic acid, washed and dried -Kurde. The sample was then bathed for 20 seconds in an activity composition composed of:

3-inolar calcium bromide solution 100 ml

3 molar copper (II) nitrate solution 50 ml

Water 850 al

-—12

■ · -, 1O98AS / 1B92

BATH

The sample was then treated with the observation solution from Example 1 rubbed in, colored in and used for printing * Gute, litho «· graphic copies were obtained.

Example 7

A sample was produced according to Example 6: under Use of nickel (II) hexacyanoferrate (II).

Solution a

LfIi

. Water ~ 95 ^ml -

0.1 molar aqueous Kickel- (II) w

nitrate hexahydrate solution 5 ml

Solution b

Water 85 ml

15 ml

water

0.1 molar aqueous potassium hexacyanoferrate (II) solution

Solution A was added to solution B with vigorous stirring. The sample was exposed to light as indicated in Example 1, developed and activated. Tray treatment with ink, good copies were obtained in printing. .

Example 8

According to Example 7 , a sample was produced using a coating which had been prepared from the following solution:

Solution a

0.1 molar aqueous solution of potassium citrate 10 ml

0.1 molar aqueous Hickel (II) nitrate

solution 5 ml

Water 85 ml

1098A6 / 1692

203S342

Solution b

0.1 molar potassium hexacyanoferrate iil solution 15 mL

Saponin (10% solution in an alcohol-water mixture) se hung) 1 ml

l ^T hymol (.5 g / 100 mL alcohol). 2 ml

V / ater "■" 82 ml

The sample was 3 seconds through a line and halftone test negative with an ITr. 2.RB ¹ L-FOtO floodlight lamp exposed, which worked at 15 volts and kept vrarde at a distance of 101.6 cm. The exposed sample was -30 sec. In |

a 1-phenyl-3-pyrazolidone / hydroquinone developer from developed high pH, washed with water for 10 sec. and activated for half a minute in an activator solution of the following composition:

3 molar aqueous Zupfer (II) nitrate solution 50 ml

3 molar aqueous citric acid solution 50 ml

3 molar aqueous potassium bromide solution 5 ml

1 molar aqueous iron (Ili) nitration solution "5ml

Water rest to 1ÖÖÖ eü.

The sample was then washed and used for 1400

Make copies in an offset office copier ', where ^ j

the humidifying solution of the example Ϊ was applied.

Good offset copies were obtained. ■ '' ■ ■ '

Example ff

A nickel (II) hexacyanoferrate (II) sol is used as follows manufactured: . ·

Solution A. - -

0.1 molar aqueous potassium citrate solution 20 ml

0.1 molar aqueous. Nickel- (II) -nit rat-

solution 10 ml

Water 170 ml

'/ 1 582-. . · ■■. ^f ■ - ■ - -

Solution B

0.1 molar potassium hexacyanoferrate (ILO solution "3® ^J nl

■ Partial sodium salt of IT-laxityl-beta-iaiao- ·. · .- ·. -. ; ... .- " _: dipropionate (1 g / 100 ml alcohol) ', 4 ial

Water . / 166 oil L.

The solution A v / became the solution B within 15 seconds, under * strong HSI hardening added. ·

A highly sensitive, locally sensitized. Gel silver godtaomide emulsion has a content of about 1.2% by weight of silver iodide, which contained about 120 g of gelatin per mole of BiX over halide and, under setting, a weight of about 25 mg / dm on a. smooth photographic carrier paper covered with polyethylene? When it was cracked open, it was coated with a sol '; smear-coating with a content of 2.44 m / Hin, and dried with hot air.

The samples were through a. Stroke isiidHplbtonr test negative with the help of a 500 Va; tt 3aP-2-lOtospotlamp e exposed at 15 volts below. worked at a distance of 127 cm. The exposed et en., Samples wiardea 20 SeM, in .dem Developer of Example 1 ent'aficlteli; rinsed in water for 5 seconds, then 20 seconds in an iOrtivätorlösung with adjusting composition-activated: -.

3-molar aqueous potassium carbonate solution: _.- .: ■; ... ■ "I5 -ail · .. 3-molar aqueous copper (II) nitrate solution 25 μl 3-molar aqueous citric acid solution"'■"'' ■ ---" ■■ 2S iu. 1 molar aqueous Sisen- (III) -iöitratnönan'-. ' ■

hydrate solution · "- ^ jf.; ■■ · .; ■: -" ■ _- 25 ΐΛ

> V - Sest 'asa "-i", triphenyl guanidine (. 1 g / 100 wl ^{-Äfeohol): -:} - ·;; "■ × 50 mL of water"■' ■■ '. <..... 1000 ml

The activated plate v / ur.de 5, Se.k ·, bit hater, rinsed, inserted into an offset office copier, rubbed in with the control solution from Example 1 .uiid td ^; a; 2; u; "entwined" to print more than n5ÖÖ offset copies "■ -.vi

jBAI> ORIGINAL

Example 10

As indicated below, a nickel (II) hexacyanoferrate (II) sol manufactured:

KsmigA

Water 800 inl

lickel (lI) nitrate! iexafcydrate 0.75 S

Ealium citrate mono1iyäj? Afc 0.61 g

Solution b

■ '= ■■■■.

Water I 190 ml

Kai iumhexacyanof errat- (II) -trihydrafc 1.06 g Nat r iumo c tylpheiiosyäifelioxy sulfonat

(4.2% aqueous solution) 10 j £ L

Solution A is quickly added to solution B while stirring vigorously. -

Example 9 was repeated using the sol described above as a coating. It is an excellent one A lithographic had received that could be used to print several thousand offset copies.

Example 11

Example 9 was repeated using an iktivie solution of the following ZiosaiBinensetzxtng: '

Glacial acetic acid 100 bü

Benzotriazole (lg / 100 si alcohol) 100 πα

1 molar aqueous potassium citrate solution 100 m ±

3 molar aqueous EaliumbroiaiG solution 50 sl

3 molar Eupfer (H) nitrate trihydrate. solution 25 inl

1 molar iron Cl33l) -mitratiapnohydrate-

solution 25 ml '

Triphenylguanidiii (ig / 100 ml alcohol) 50 vü.

'Eest: ,, ¥ ater to IpOO eI

A good lithographic plate was obtained which was quick to operate on the press
excelled without any sub-surface foam occurring.

Example 12

Example 7 was repeated with the exception that the activator solution had the following composition:

3 molar aqueous Kiipfer (II) nitrate trihydrate solution

3 molar aqueous potassium bromide solution 1 molar aqueous potassium acetate solution 1 molar aqueous potassium citrate solution

1 molar aqueous iron (III) nitrate monohydrate solution

Rest: water too

Good lithographic ink prints were obtained.

Example 13

Example 7 was repeated with the exception that the activator solution had the following composition:

3 molar aqueous copper (II) nitrate solution 50 ml

3 molar aqueous citric acid solution 50 ml

3 molar aqueous potassium bromide solution 5 ml

1 molar aqueous iron (II) nitrate solution 5 nl

Remainder: V / water to LOCO rill

Good lithographic ink prints were obtained.

Example 14

As indicated below, a nickel (II) hexacyanoferrate sol made:

12th , 5 ml 25th ral 100 ml 100 ml 100 ml " 1000 ml

10984B71S92

Solution A.

Water ■ 665 ml

0.1 molar aqueous nickel (II) nitrate

hexahydrate solution ■ 20 ml

0.1 molar v / aqueous potassium citrate mono-

hydrate solution 15 ml

\ ■

Solution B

Water . 72 ml

0.1 molar potassium hexacyanof errat- (ll) -

trihydrate solution '20 ml

Condensation product of coconut fat acid and diethanoiamine (lg / 100 ml... alcohol) ■ 8 ml

Solution A became solution B over the course of 15 seconds strong IS added to it at 24 ° G.

A commercially available one is inserted into this sol Magnifying paper immersed in the photosensitive emulsion of which developer was incorporated; the sol was drained and dried.

A sample was through a negative line and halftone image transparency for 10 seconds using a KaM ^r J? Ri Level Point Source lamp, a 100 watt tungsten filament lamp from General Electric Co. operating at 8 volts (Type: Flash 100 T 8-15c-20v) exposed, a setting of 1 and a distance of 139 »7 cm being maintained. The exposed sample was treated with a basic activator solution for 30 seconds and then with the lithographic activator solution of Example 9 for 10 seconds. good lithographic copies are used.

10984SMS92

Example 15

The emulsion of Example 9 was applied with a layer weight of about -25 mg / dm to a smooth, polyethylene-coated photographic paper and dried Example 10 _{overlays 5 to} which 40 g / liter x-hydroquinone and 5 g / liter sodium sulfate were added. Up to the sample, it was popular according to Example 14, with the exception that an exposure time of 3 seconds was adhered to. The exposed sample was further treated as in Example 14 and a good lithographic copy was obtained.

Example 16

According to the specifications of the USA patent 3 ^ 5 235, a directly positive cliled silver chloride emulsion was prepared and, according to the setting of a layer weight of iron, 57 mg silver halide / dm was applied to a polyethylene terepat neck Irägerfllin, the preparation of which is given in Example 4 of the USA patent 2 779 684, _{see p} after which, dried wo? de. The esmlsin was then covered with an ifickel- (II) -hexacyanof errat- (II) ~ 3ol of Example 5 at 2 _for 4 m / min, and 38 ⁰ G under a red safety light. then dried with telße3g air.

A sample was 20 S © fc. exposed by a positive line and halftone image transparency with a 500-¥ att-EFL-l'otoflu.tampe, which operated at 110 volts at a distance of 0-61 m & ■. The exposed sample was developed for 30 seconds in the developer of Example 1, rinsed with water for 5 seconds and active for 20 seconds with the activator solution of Example 9 After treatment with the moistening solution of the example, the plate was used to print good positive lithographic printing ink copies. ■ _ _1Q __

,. BATH ORIGINAL

109345/1592

Example 17

A sample of the material of Example 16 was through a positive line and halftone image transparency with a 500 watt HFL photo floodlight lamp that exposed at 110 volts and acted at a distance of 0.61 m for about 20 seconds. The sample was then 30 Sak. at 23 ° C in a 1-piienyl-J-pyrazolidone / hydroquinone Kntwiekler of high pH, containing 0.25 g / l benzotriazol and 0.5 g / l 1-gyanoguanidine. The developed sample was in. 8 sec. At 23 ° C an activator solution of the Her- ^ described below position activated.

First, solutions A and B were prepared.

Solution a

3 molar aqueous copper (II) nitrate trihydrate solution

3 molar aqueous potassium bromide solution 3 molar aqueous citric acid solution 1 molar aqueous iron (II) nitrate solution Eest: V / ater closed

Solution b

1,10-phenanthroline. (Ig / 100 ml alcohol) 1,2-bis (2-chloroethoxy) ethanol

The activator solution corresponded to the following preparation location:

25th ml 15th EÜ. 25th ml 10 Hurry 900 ml 50 ml 10 ml

Solution a V / ater too 900 ml Solution b 60 ml Rest: 1000 ml

The activated plate was sucked dry on an office copier with the humidifying solution of the example 1 wobbled and for printing several hundred Di-uci color copies verv / ends - Good positive lithographic 'images were made obtain. .

109845/1592 ■

Example 18

Was erephthalat ethyl ent on a photographic Tragerfilm of poly a highly sensitive, ortho-sensitized silver iodobromide gelatin emulsion coated which had ^v Iol .-% 3ilberJodid 1.2 I IMD in a gelatin: silver ratio of 0.36 was present, a coating weight of 7 ₅ 2 mg silver bromide per dm was set. The emulsion was -überzogen layer having a Abriebschutn, templates in the luh mg / dm ^ gelatin 2.96 g of formaldehyde and 11.25 g per 100 g of gelatin material Dimethylolharr- waz cured ^v s. The ε-material was then covered with the ITicltel— (II) hexacyanoferrate (II) sol of Example 10 with coating at 38 ° and 2.4 m / min, and dried with hot air.

A sample of the material was taken through a step sink and Line art transparency 10 seconds with a KaLi Tri Level Point source lamp that worked with a setting of 2 at a distance of 127 cm (same light source as in Example 14, voltage: 16 YoIt) exposed. It was an ultraviolet filter and a neutral density filter of 0.6 optical density were applied. The exposed sample was developed in the developer of Example 1 for 30 seconds and Activated for 8 seconds in an activator solution with the following composition:

3-molar Eupf ER · (II) -nitrattr i hTciratIosung 3 molar ICaliumbromidlösung 3-molar citric acid solution

1 molar iron (III) nitrate nonobydrate solution

Rest:. Water au

The plate was then rubbed with a 1; - ^ - strength aqueous dispersion of colloidal SiOp, uixd on oii'jer. ^1st Bürokopiergeryt used to print offsot / opicn cu,

10S8U / 1592.

ORDINAL

25th ml 15th ml 25th ml 10 ml 1000 ml

where the printing ink and the moistening ^ solution of the case game 1 were applied.

A sample of the coated emulsion of the example was by bathing in a palladium (II) hexacyanoferrate (II) sol overlaid as indicated below was made, after which it was dried:

Lp'sunp; A.

Water "■ ... 665 ml

0.1 molar aqueous palladium (II) -. Chloride solution 20 ml

0.1 mplare aqueous potassium citrate

solution - 15 ml

Solution b

Water 72 ml

0.1 molar Ealiumhexacyanoferrat-

(II) solution 20 ml

Condensation product of coconut fatty acid and diethanolamine (lg / 100 ml

Alcohol) 8 ml

Solution A was quickly added to solution B at 2 ^z ! - ° ö with vigorous stirring.

The sample was exposed through a step wedge at a 0.0001 -3 ek.-31it ζ mib in an Edgerton, Germeahausen & Grier-Hark VI exposure device. The exposed sample lasted 30 seconds, unraveled in the kit developer of Example 1, vacuumed for 5 seconds and activated for 15 seconds with an activator solution of the following composition:

3 molar aqueous copper (II) nitrate solution 25 oil 3 ™ Hiölar aqueous potassium bromide solution 15 ml 3-molar aqueous citric acid solution 25 al Remainder: water to 1000 ml

"- - 22 -

, 10384S / 1832 _SA0

The activated sample was with the * humidification of the Example 1 buffed and then treated with lithographic ink; there are good lithographic Eopies obtain.

Example 20

Example 19 is repeated with the exception that fifeo & iuci (II) chloride instead of palladium chloride was used. Gate lithographic copies were obtained.

Example 21

A material produced according to Example 10 was exposed on a photographic device which had a cathode ray tube reading and which operated under the conditions which are normally required for the exposure of I ^? otoprint film ice cream. can be applied. The exposed sample i-airde developed for 30 seconds in a suitable developer device, which is filled with the developer of the; Example, 1 was filled, after which S sec. Was activated in a suitable processing machine which was filled with the activator of Example 9. ISanmefar tzurde the sample was placed on the office copy aiascoine of Example 1, with the dampening solution of Example 1 setofabbelt, colored with lithographic BniclEfarben and used to print several hundred copies of good quality on hard paper.

10984S / 1S92 BAD ORJÖlNAt

Claims (10)

PATENTAKWÄ '.- E DR-IN G. VO U KREISLER DR.-lNG. SCHÖ NWALD 2Q 3 8 3 1 DR.-ING.TH. MEYER DR. FUES DIPL-CHEM. ALEK VON KREISLER DIPL.-CHEM. CAROLA KELLER DR.-ING. KLOPSCH COLOGNE 1, DElCHMANNHAUS Pat ent ann-oruche 2> * ty Photographic material, consisting of a layer support with an overlying, water-permeable, protein-containing layer of a colloidal silver halide solution, characterized in that a layer consisting of a hexacyanoferrate is effectively associated with the surface of the emulsion layer, which contains a SchliermetaXl-3! exacyanoferrat (II) or a heavy metal-HexacyaaoJ: errat (III). 2.) photographic material according to claim 1 , rla & rrch ge ™ indicates that the heavy metal copper (II), nickel (II), Eobalt (II), palladium (II) or Hhodiun (II) xst. 3.)! Photographic material according to claim 1 uaö 2-, thereby characterized in that the layer containing the ilexacyanoferrate lies in or on the surface of the emulsion layer. 4.) Photographic material according to claim 1 to 3 Ouad 2, characterized in that the eexacyanoferrate containing Layer on a thin layer that is adjacent to the emulsion layer water-permeable, abrasion-resistant, colloid interlayer made of protein. 5-) Photographic material according to claim 1 to ¹ U-, characterized in that the hexacyanoferrate is a 1! IeKeI- (II) -hezacyanof errat (II) or a Kickel-ClIy-hesacy ^ aoferrate (III). 6.) Fotografisehes Katei-ial according to claim 1 - 5 _S c-a characterized by, ■ da5- the layer support a Pila aua eii-.erc b "lrophobon _t macroinolelailai-eii, or ^ ariiKchen PoijSiei ^ cii i 109846 / 1.592 7.) Photographic material according to claim 1 to 6, characterized characterized in that the layer weight of the silver halide is at least 1 mg / dm, preferably 5 to 50 mg / dm. 8.) Photographic material according to claim 1 to 7 »■ thereby characterized in that the emulsion is an orthochromatic gelatin-silver halide emulsion. 9.) Photographic material according to claim 1 to 8, since * characterized in that a photographic developer is present in the emulsion. 10.) Process for the production of lithographic printing * plates by imagewise exposure of a silver halide emulsion layer photographic material containing actinic radiation, Jäitwickluäg des in the latent SiXberhalide image present in the emulsion layer, Treatment of the developed layer with an aqueous solution containing copper (U) ions, and transform the developed silver image into silver ions au, whereby the exposed areas of the emulsion layer become receptive to oily printing ink, characterized in that the photographic material after spoke 1 to 9 begins. 109845/1592