DE2634196A1 - FLAT PRINT PLATE MATERIAL - Google Patents

Description

The invention relates to a planographic printing plate material, i. a lithographic printing plate, particularly one that is non-treatment Planographic printing plate material that after exposure can be used in a printing machine without any treatment.

In the description, as is generally _customary} both the material for producing the Fiachdruckplatte, and designates the Iflachdruckplatte made of this material as "planographic printing plate." This designation also includes the exposed and developed printing plate, which is also referred to as "printing forme ¹¹ ".

As Flachdx-pl & tten have so-called deep-etched plates and presensitized plates found widespread use.

ORIGINAL INSPECTED

709807/1041

TELEPHONE (OSQ) 22 28 60 TELEX OÖ-2f * G3O TELEGRAMS MONAM TELECOPY F3

The manufacture of deep-etched plates is carried out by the Steps: Applying a layer of photosensitive resin to a grained aluminum or zinc plate, developing after copying a positive original from it, rubbing in a tincture after or without etching, applying one Varnish thereon, and then peeling off the hardened photosensitive resin layer.

On the other hand, presensitized plates, hereinafter referred to as PS plates, mainly constructed in such a way that a light-sensitive Harεschicht is on an aluminum plate is located. In the case of such PS plates, the image is copied using a positive original (positive mask) or Negative originals (ITegativnaske) and developed, and then becomes a) development paint or protective varnish on the hardened photosensitive resin layer constituting the image areas, whereby the printing plate is obtained. To this It is true that the treatment stages required for the production of PS plates can be compared to the deep-etched ones Plates, greatly simplified; however, such stages as development, etc., are still required.

Recently, planographic printing plates have been proposed in which post-exposure treatments are omitted and which can be used in printing machines immediately after exposure without applying any chemical treatments. In this specification, such printing plates are referred to as "treatment-free" printing plates in the sense that no treatment as described above is applied. Such printing plates are described in detail in the known JA-PA 33 644/72.

709807/1041 offifflK «. .Νβ «ΠΗ»

These planographic printing plates are made from a radiation sensitive Element made of the three-layer structure, in which a metallic first layer, a second layer of a material which is a reaction product upon reaction with the aforementioned first layer upon exposure to light able to form electromagnetic radiation, and a third layer made of a material similar to the aforementioned second layer is non-reactive, are interconnected. In this! ”All there is an electromagnetic radiation image projected onto the aforesaid second layer through the first or third layer, whereby the aforesaid seaction product is formed selectively, whereby in turn the areas where the aforementioned reaction product is formed, a different ratio of hydrophilic nature to oleophilic nature, compared to the non-reactive areas, own. In this way a planographic printing plate is obtained.

The conventional non-treatment planographic printing materials such as the above, however, have an insufficient storage side, since often an undesirable one during storage Interaction between the first layer and the second Layer of material takes place. Because, moreover, these conventional treatment-free planographic printing plate materials an insufficient ratio of hydrophilic nature to oleophilic nature In their nature, these materials cannot be used as printing plates in practice.

In the context of the investigations carried out according to the invention on the aforementioned treatment-free planographic printing plates now a printing plate, developed that 'differs from conventional Planographic printing plates, is free from various problems associated with conventional planographic printing plates.

709807/1041

and better properties than the treatment-free plan printing plates owns.

Accordingly, the invention relates to a flat printing plate material, which is characterized by a support and a photosensitive layer located on the support, the photosensitive Layer consists of an inorganic material and at least one metal and / or a metal compound (which are able to enter into a reciprocal reaction under the action of electromagnetic radiation), and an organic one Compound capable of affecting the aforementioned mutual reaction, which are in contact with each other, the application of electromagnetic radiation making a difference irradiated in the hydrophilic or oleophilic Hatur svriachen Areas and the unexposed areas of the photosensitive layer causes.

Thus, preferably, the invention relates to a I ⁷ Iachdruckplattonmaterial with a support having on the support the photosensitive layer, wherein the photosensitive layer is composed of (A) an inorganic material and (B) at least

• M-j-in j / j · η · j. -ι η τ -, where (A) and (.B) a metal and / or a metal compound, / under aer Exposure to electromagnetic radiation are able to react with one another, and (C) an organic compound which the Reaction between the inorganic material and the metal and / or the metal compound is able to affect, the inorganic material, the metal or the metal compound, and the organic compound are in contact with each other. Will the photosensitive layer of electromagnetic radiation exposed, there is a difference in the hydrophilic or oleophilic nature of the exposed areas and the unexposed areas Areas created, whereby one obtains a facing back plate,

709807/1041

which can be used in a printing machine without any treatment.

The treatment-free fla'ch printing plates of the invention differ differs very much in various respects from the well-known planographic printing plates, as in the well-known JA-PA 33 64-4- / 72 so that they can be distinguished from one another can be. Although both cases are treatment-free Is planographic printing plates, the known printing plates have a radiation-sensitive element with a three-layer Structure, while according to the invention at least one of the components of the photosensitive layer is not in the layer form, but there is an area that is always in a state of a physical mixture «, Furthermore, in the known printing plates, a metallic layer and a material layer, which become a reaction product able to form connected, while according to the invention, in addition to an inorganic material and a metal and / or a Metal compound that are reactive with each other, an organic compound that adversely affect this mutual reaction capable of being present, giving excellent printing properties. Thus, the printing plates of the invention have excellent properties.

The invention is explained below with reference to the drawings. the

Figs. 1 to 14 show schematic cross-sectional views

of planographic printing plate materials of the invention in which various structures illustrated by showing various combinations of materials.

709807/1041

Suitable carriers according to the invention are those which have a hydrophilic Have surface and suitable rigidity, e.g. 3. those used as supports for conventional planographic printing plates and those carriers which have the properties of being so used. Suitable examples are metal plates, Plastic films or plates, the surface of which has been subjected to a hydrophilization treatment, or Composite materials in which a metal plate or metal foil laminated to a plastic folio or paper.

The metal plates are generally aluminum plates or Zinc plates or so-called multilayer plates used "

When used, these metal plates are preferably subjected to roughening with sand in order to improve their water-guiding properties and to improve the adhesion between them and a photosensitive layer thereon. Similar to conventional PS plates, all surfaces are treated chemically or electrochemically after roughening, if necessary. In the case of aluminum plates in particular, an aluminum oxide layer is preferably produced on the roughened surface by anodic oxidation. It is also possible to improve the performance properties of the planographic printing plates by treating the surface with acids or Bssea.

As an electrolysis for the anodic oxidation of the aluminum plates e.g. sulfuric acid, phosphoric acid or oxalic acid are suitable. In addition, the application of a porous chrome plating to the surface of the aluminum plate has hitherto been pursued carried out the sand roughening, and it can thus obtained Trä ger can be used.

709807/1041

Examples of plastic films or plates whose surface has been hydrophilized are films or plates made of cellulose triacetate, the surface of which has been made hydrophilic by saponification, and those which are made by applying a hydrophilic layer to the surface of a plastic film ζ. B. polyethylene terephthalate, have been made.

Even in the case of using a metal surface, it is not always necessary that the entire substrate be made of metal exists, rather the carrier can partially be replaced by plastic or paper. This means that compound Composite materials in which a metal layer and a plastic film or paper are laminated are used.

In the planographic printing plates of the invention, a photosensitive layer is provided on a support, containing (A) an inorganic material and (B) at least one metal and / or

does o. -, π ι_ · ο / (A) / (B) are _. . . TiJ. j. · -L. a metal compound, reactive with one another under the action of electromagnetic radiation, and (C) an organic compound capable of impairing the aforementioned mutual reaction.

Inorganic materials, chalcogens, chalcogenide masses are used as (A) and halides are used.

The chalcogens are elements of the Schkefel group, i.e. S, Se and Te, as well as mixtures thereof.

Chalcogenide masses that can be used are those of the formula M-sulfur group element, M-Schw.ef.elgruppeelement-X, M-sulfur group element-Z-Y, etc. can be applied. In this case, M means an element from the group As, Sb, Bi, Ge, Sn, Pb, In, Cd, Cu, Zn, Ag, Ti, Fe, Cr, Tl, Hg and Si, preferably Ge, Sn, Pd, Ag, Ti,

709807/1041

le, Si., X and Y, which do not have the same meaning as M, each mean an element from the group Al, Sb, Si, Mg, Ti, V, Mn, Co, Hi, Ta, Mo, W, Sn, Zn, Pb, Bi, Ag, Pd, In, 0, P, Cl, Br and J. Furthermore, X and Y can be an element from the group S, Se or CPe, which are not represents the same as the sulfur element group of the aforementioned formulas. Preferably X and Y each have the same meaning Bi, Zn, P, Pb, O, Mn, Se, Te. Examples of chalcogenide masses are As-S, As-Se, As-Te, Ge-S, Bi-S, Sb-Te, As-S-Te, As-S-Se, Ge-S-Bi and Ge-S-Bi-Si .

Examples of halides which can be used as an inorganic material dor the invention are those compounds which contain a halogen atom (ie Cl, Br, I) and an element from the group consisting of Cu, Zn, Cd, Hg, Tl, Pb, Sb, Bi , Ge, Sn and In. Specific examples of such halides are Cu, Br ₂ , AgCl and PbCl.

Of these inorganic materials, those compositions which contain germanium and sulfur are particularly suitable according to the invention, namely because compositions containing germanium and sulfur have a lower toxicity and cause only low environmental pollution; In addition, it is comparatively easy to regulate the hydrophilic and oleophilic properties. The preparation of germanium and sulfur-containing masses is carried out, for example, by weighing out germanium and sulfur, and possibly other elements or compounds as starting compounds in such amounts that the predetermined atomic ratio is achieved, and then placing them in a silicon dioxide capsule under a pressure of 10 ^J Torr fills. This is followed by heating until it melts and then homogenizing the molten solution by keeping it for a longer period of time

709807/1041

keeps melted. Then the silica capsule is quenched in water or cools down to room temperature in a tree. Of course, starting materials can be used instead of germanium and <sulfur elements, masses containing both elements are also used, e.g. germanium sulfide.

Examples of germanium and sulfur which are suitable according to the invention containing compositions are given below.

Based on Ge-Si. GeS, GeS ₁₅ , Ge ₃₅ Sg ₅ , 'GeS ₂ , GeS ₄ and Ge S Auf Bnsis Ge-SX; Ge ₇₅ Sg ₀ Al ₅ (amorphous), Ge ₅₅ Sg ₀ P ₅ (amorphous), Ge ₅₅ Sg ₀ Sb ₅ (amorphous), Ge ₅₅ Sg ₀ Si ₅ (amorphous), Ge ₅₅ Sg ₀ Mg ₅ (amorphous + crystalline ), Ge ₅₅ Sg ₀ Ti ₅ (amorphous + GeS ~ + TiSp), Ge ₅₅ Sg ₀ V ₅ (amorphous + GeS ₂ + V ₂ S ₅ ), Ge ₅₅ Sg ₀ ItI ₅ (amorphous + Mn ₂ GeS ₄ ), Ge ₅₅ Sg ₀ --Co ₅ (amorphous + GeS ₂ ), Ge ₅₅ Sg ₀ Hi _n (amorphous + GeS ₂ ), Ge ₅₅ Sg ₀ Ta ₅ (amorphous + TaS ₂ ), Ge ₅₅ Sg ₀ Mo ₅ (amorphous + MoS ₂ ), Ge ₅₅ Sg ₀ W ₅ (amorphous + WS ₂ + crystalline), Ge ₅₅ Sg ₀ Sn ₅ (amorphous + ß-SnSp or oil- ^Sn 1 + x ^S 2 ^ ^{? Ge} 35 ^S 6O ^Zn 5 (amorphous + ZnS), Ge ₅₅ Sg ₀ Pb ₅ (amorphous + GeS ₂ ), Ge ₂₅ S ₇₀ Bi ₅ (amorphous), Ge ₂₀ S ₇₀ Bi ₁₀ ( ^6111103 ^ P ¹¹ ) » ^Ge io ^S 8O ^Bi 1O (amorphous), Ge ₁₀ S ₇₀ Bi ₂₀ (amorphous), Ge ₂₀ S ₈₀ Bi ₁₀ (amorphous), Ge ^ ₀ Sg ₀ Bi ₁ (amorphous), Ge ₅ S ₈₀ Bi ₁₅ (amorphous), Ge ₅₅ Sg ₀ Bi ₁₀ (amorphous + Bi), ^Ge 35 ^S 6O ^Bi 15 (^ ⁰¹¹ P ¹¹ + Egg) »Ge ₄₀ S ₆₀ Bi ₅ (amorphous + Bi), Ge ₄₀ S ₅₀ Bi ₁₀ (amorphous + Bi), Ge ₅₅ Sg ₀ Bi ₃ (amorphous + Bi), Ge _{58 4} gSg ^ 54 ^Bi 5 (amorphous + Bi), Ge37 _i7 Z]. ^S 62.26 ^Bi 5 ( ^{810 01} P ^{11 + Bi} h Ge ₅₁ ^ Sg ₈ ^ Bi ^ (amorphous + GeS ₂ ), Ge ₂₀ Sg ₀ Bi ₂₀ (amorphous + GeS ₂ ), Ge ₁₀ Sg ₀ Bi ₅₀ (amorphous + Bi ₂ S ₅ )

709807/1041

- ίο -

Ge ₄₀ S ₆₀ Bi ₁₅ (amorphous. + Bi + GeS ₂ ), Ge ₁₀ S ₅₀ Bi ₄₀ (amorphous. + Bi + Bi ₂ S ₅ ), Ge ₅₅ S ₆₀ Bi ₅ (amorphous + Bi + GeS ₂ + GeS) , Ge ₇₅ S ₆₅ BI (amorphous + Bi + GeS ₀ + GeS) _{, Ge ^ 7 7} S _ac - ^ Bi. _r (amorphous + Bi -s-

<- JJ » J OO, ( I J

GeS ₂ + GeS), Ge ₂₀ S ₅₀ Bi ₅₀ (amorphous + Bi + Ge ₄₅ S ₅₀ Bi ₅ (GeS + Bi), Ge ₂₀ S ₈₀ 0 _0i2 , Ge ₂ Ge ₄₂ S ₅₈ As ₂ , Ge ₅₆ S ₅₅ J ₉ , Ge ₃₅ S ₆₀ Al ₁₅ , Ge ₂₀ S ₇₅ Al

₇₅ Al ₅ ,

and Ge ₂₅ S ₅₀ Sb ₂₅ .

Based on Ge ^ -S- XY: Ge ρ, -Si, ^ ₀ S ₆₀ Bi, - (amorphous + Bi), Ge ₇₀ Si ₁ -S ₆ QBi (amorphous + Bi + GeSp), Ge ₀₀ Si ₁₁ -S ₆₀ BiJ- (amorphous + Bi + SiSp), Ge ₁ C-Si ₂₀ S ₆₀ Bi (amorphous + Bi + SiS ₂ ), Ge ₁₀ Si ₀ JS ₆₀ Bi ₁ - (amorphous + Bi + SiS ₂ + BipS ₅ + GeSp ), Ge ₅₅ Sc ₇ Bi _n Ag ₁ - (amorphous + Bi), Ge ₅₀ S ₆₀ Bi ^ A (amorphous + Bi + GeS ₂ + GeS), Ge ₅ ^. ScqBij-AG ^ (amorphous + Bi + GeS _p + GeS), Ge ₅₅ S ₅₇ Bi ₅ O ₅ (amorphous s- Ei), Ge ₂₀ Sg ₀ P ₁ O ₂ , Ge ₂₀ Sg ₀ P ₁₀

^Ge 20 ^S 60 ^Sb 5 ^P 5 ' ^Ge i5 ^S 7O ^Sb 7,5 ^P 7,5' ^Ge io ^S 8O ^P io ^Pb o, 5 ^'00 IO ⁸ SO ¹

^Ge 10 ^S 80 ^P 10 ^Bi 10 ' ^Ge 55 ^S 6O ^P 5 ^Bi 5 ^and

The numbers which show the composition ratio of the aforementioned masses give the atomic ratio of the starting materials and since some of the aforementioned masses are not normalized, the total sum of the numbers sometimes exceeds the value '10O. The oxygen-containing masses are produced in such a way that that one melts oxides as starting materials. The information in brackets qualitatively indicate the results that obtained by means of X-ray analysis of the masses obtained; some masses are amorphous and others partially or completely crystallized. The use of such masses allows

709807/1041

the production of the printing plates according to the invention.

The composition ratio of the. Containing germanium and sulfur Masses are in the range of 1 <S / Ge <16, preferably 1 < S / Ge <9

Metals (B) suitable according to the invention are Ag, Cu, Ge, Zn, Cd, Au, Pb, Al, Ga, In, Sn, V, Se, Cr, Fe, Tl, Bi, Mg, Mn, Co, ETi, Sb, Te and Pd. Here, Se and Te are used as the metal of (B) when the inorganic material (A) is a chalcogenide component or is a halide. Suitable examples of the aforementioned metals are Ag and Cu.

Metal compounds used according to the invention as (B) are sulfides of metals from group IB, II B, IV B, VB and VIII; Group IV, V, or VI metal oxides; or halides of metals of Group IB, IV B or VI B (these halides are used when the inorganic material (A) is a chalcogen or a chalcogenide component) of the periodic table. Above, halides and sulfides of metals of group IB, IV, B or VIII of the periodic table are suitable. In particular AgCl, AgBr, AgJ, CuCIp, CuBr _? , PbCl, PbCIp, AgS, CUpS, PbS and IeS are most preferred.

According to the invention, compounds (C) are organic compounds (C) suited to those in the field of halosilver emulsion photochemistry Find applications such as antifoggants, desensitizers or sensitizer dyes. Beyond that, you can organic photochromic materials can be used.

Examples of suitable organic compounds are given below.

709807/1041

.τ

I. Aldehydes and Ketones

(1) Aldel ^ de of the general formula

ECHO (R «H, methyl, ityl, phenyl)

such as formaldehyde, methylaldehyde, acetaldehyde or benzaldehyde;

(2) Hydroxyaldehydes of the general formula HOEGHO (E = C _1-5 -AlCyI) such as glycolaldehyde or aldol;

(3) halogenated aldehydes,

such as mucochloric acid or mucobromic acid;

(4-) unsaturated aldehydes,

such as acrolein or crotonaldehyde;

(5) oC diketones of the general formula

ECOCOE ¹ (E, E ¹ = C _1-5 -alkyl, phenyl),

such as diacetyl, acetylbenzoyl or dibenzoyl;

709807/1041

(6) ß-diketones,

such as acetylacetone, benzoylacetone or dibenzoylacetone;

(7) tf diketones,

such as acetonylacetone;

(8) oC-ketoaldehydes of the general formula

RCOCHO (R = methyl, ethyl, phenyl, p-bromo ~

phenyl),

such as methylglyoxal, acetoaldehyde or phenylglyoxal;

(9) acetals of the general formula RCH (OR ¹ ) ₂ (R, R ¹ = C 1-4 alkyl), such as diethylacetal;

(10) Hydroxyketones of the general formula RCOC (R ¹ ) (R ' ^! ) CH ₂ 0H (R, R ¹ , R "= such as 2,2-dimethylbutanol-J-one;

(11) reaction products from formaldehyde and amines,

such as "condensates of hexamethylenetetramine, formaldehyde urd Benzimidaseole, phthalimide, etc .;

709807/1041

II. Alkylene Oxide Polymers

(1) HO (RO) _n H (R = lithylene, propylene, butylene t

η = 10 to 10,000);

III. Carboxylic acids

(1) lower unsaturated carboxylic acids,

such as maleic acid, fumaric acid or cinnamic acid;

(2) EDTA, i.e. ethylene dianiine tetraacetic acid.

IV. Phenols

(1) Phenols and derivatives of the general formula

^0H (R = H, methyl, ethyl, COOR ¹ , where

_R R ¹ = methyl, ethyl),

such as phenol or hydroxybenzoic acid p-methyl ester;

(2) polyhydric phenols of the general formula

OH

(R = H, C. .p

OH-

like hydroquinone, methylhydroquinone, propylhydroquinone

or 2,5 ~ di (1,1-dimethylbutyl) hydroquinone; 709807/1041

V. Amines "and Hydrazines

(1) aliphatic amines of the general loriael

HH ₂ (EHH) _n ENH ₂ (E = G _1-6 alkylenes; η = 1 to 3), such as 3-azatetramethylenediamine;

K <CH ₂ O _n HH ₂ (n = 1 to 20), such as β-phenylethylamine or tr-phenylpropylamine;

(CH (E) HH ₂ (E = C _1-5
such as 1-phenylpropylamine or 1-phenylbutylamine;

(2) aromatic amines such as those containing two or more amino groups in a benzene ring, such as

Benzidine, chloramine or mead oil;

(3) hydrazine

VI. Such compounds that contain an HH-CO group, such as

Phthalimide, saccharin, salicylamide or acetylated compounds of aminophenols

709807/1041

VII. Swarms! containing organic l'erbirjcmnyen, organiHch-v; Yerbine anger! _v with at least one -SB group> ^ G- "S-group _Ϋ - ~ (S) n ™ group _? where η has a value from 1 to G bat, -SÜ-Vl --- group or ~ SO ₇ Ii- Gruppo 3d ^: can be used for wet use.

(1) I'Moliamstoff the general li? Ormel

R ¹ SK ^ (E ¹ to E ⁴ = JI, alkyl or% dro:> - y ~

IT-G-N 'alkyl with 1 to 5 carbon atoms, phenyl,

V? ^ R ^ where ifl and Ii ^ or Ώ? uud E ⁴ with-

each other forming a five ~ jointed hcfcorocycliGehen Κίη ^ ΰ, uae pyrrolidine, dies t his hüanen),

like Siiioliarnstoxf, ^ thjlcnthiourstoff, Srimetliylthr "oharnntoff odar U, lf ^f » Iiinetliyloltbioharnstoi: f \

(2) xhioseraicarbasid and thiocarbasid of the general ! • Ormel

up to E ⁴ = H ₅ phenyl),

R ¹ S

and LcrivKts bicrton, such as thiosar-i-zrarbazid, 4-phenyl- ■; / hiOf: -c - :: ic "\ rbaz-id. Dithizone or thiocarbazide;

7098 0 7/1041

BATH ORIGINAL

(3) Sulphides or polysulphides of the general formula

Ε ⁴ ~ (8) _Β ~ Ε ² (R ¹ , E ² «C _1-30 -AIkJl, phenyl,

Naphthyl; being these groups
can be substituted with
a carboxyl group, ITitro group,
-HHp- group, Fornylalkylaraiu.0 group with 1 to 3 C-atoms, etc .;
η = 1 to 6)

like ^l \ , ^ '- thiodibenzoic acid or Di for my Im ethyl di-SU If id

(4) Sulfinic acids or sulfonic acids of the general formulas

E-SO ₂ H (E = 1 to 5 alkyl, phenyl),

E-SO ₃ -H

such as benzenesulfinic acid, benzenesulfonic acid or 2-butane sulfinic acid;

(5) Dithiocarbamic acid of the general formula

S] ( ^r1 > B ^{2 β} Η » ^c ^ b" ^A11 ' ^y1 ' °° 7-9 "

ti

-CS M ⁿ aralkyl, phenyl; H = H, n-valued

Metal ion; η = 1 to 2) η

y ■

such as Sodium disbhyldithiocarbamate .., P-silverdiHthyldithio · carbp.iaat or ZirjJfcdibenzyldithiocarbaiaat;

709807/1041

ORIGINAL INSPECTED

(6) iDhiobcniiophciioii dtr al Ig ..feinen. formula

Ii ¹ , E ² = H,

Alkoxy, amino group, substituted ι - '·. t 'two alkyl groups each with 1 to 5 carbon atoms, 01, Br ₅ J) ₅

like Ν, ΙΤ, ΪΤ ¹ , 1T ¹ -QJetraraetb-j: '.- ". Λ ^χ -diaiLinothiolsc-nzophenon (Tliio-ίϊά chiGrs .-.'! CgI; on);

(7) Five-membered tings or derivatives thereof with one Sulfur atom as Einübectaii & part

(a) Ditliiolaii.

(b) thiazole or bensothiazole, which may be substituted can with an alkyl group with 1 to 5 carbon atoms., an Acetyltliioacetaraidogrupps, an -EHp-Gcupps and / or an -SII group, if desired :;

like 1,3-thiazole, benssothioazole, 2 ~ Ai: iinobonsothiai'oi ₅ 2./A- (AcetyltM.o) -acet ^ & Piiäo / ~ ben? .othiasol? 2-Iiepcaptcbenzothiasol or 2-MGrc; .pto-6-iaetlijlben :: othia2ol;

(c) egg azoline, rhodanine or isorhodanine;

(d) i'hiaaolidine or 4-carboxythiazolidine;

(e) Thiadiazole, 2,5-I ⁱ iM-j "capto-1,37 ^ -thiadiazol or

Potassium ™ ^ -;:; alxid-2-tliic3C0 "1,3, ^/ 4-thia« iir- .. 'rclin

709807/1041 ORIGINAL BATHROOM

Five-membered compounds containing Bieao Schv-efel: ndur, gen _i can be unsubstituted or substituted. Of these, mercapto or thioether-substituted compounds are particularly preferred »

(8) Div- the following compounds, substituted with one --SH-Gruppe, «S-Gxmppe odor -S - E-Gruppe, where E is a Alkyl or alkenyl group with up to 20 carbon atoms., one; Phenyl group or the like. means;

(a) pyrrole and bensopyrrole; the substituted; be can with an alkyl group with 1 to 20 carbon atoms, e.iner phenyl group υηα / or an alkylcarbonyl group with 2 to 5 carbon atoms, if desired;

vrie 2-liercaptopyrrole or K-mercapto-2-acetylbenzopyrrole;

(b) imidazole and benzimidazole; which are substituted can with ein.i? Alkyl group with 1 to 20 carbon atoms, an alkylamido group with 2 to 21 carbon atoms imd / - or phenyl flu, if desired;

like 2-hercaptoimidazole, 2 ~ mercaptobenzimidazole, 5-lauroamido-2-raercai> tobenzimidazole, 2-undecyl-3 ~ phenyl-4-mercaptoimidazole or i-phenyl-2-me-rcaptoimidazole;

(c) Imidaζ ο1in e,

like 2-hercaptoimidazoline or 2-Kc: £ lyldecylthioimidazoline (Hydro bromidsals);

709807/1041

ORIGINAL INSPECTED

(d) pyrazole and fjr-azolidine; which are substituted
can have 1 or more carboxyl groups and / or benzoyl groups, if desired,

like 1-Hercaptopyrazol, 1 ~ Mercaptopyr8.sol-? _Y 5'-ö.i carboxylic acid j 1 ~ bensoyl ~ 3 ~ risreaptcpyrazolidine
or "i, 2-Benzoylpyraz-olidin-3-thione;

(ο) Triazoles and Benzotriazoles, which can be substituted rait 1 or two alkyl groups with 1 to 20 Carbon atoms, a phenyl group and / or phenyl group substituted rait an Alkylaniidofpr-group with 2 to 20 carbon atoms, if desired;

like 2-Hercapto-1,2,4-triasol, H-Kercaptobeasotris. "

4-phenyl-5 ~ aercaptotriazole, 3-kercapto-4 ~ pli? Iiyl «1,2,4 ~ triaaol, 3-p-caproamidophenyl-4" ethyl ~ 5-5 acrcapto-- Λ , 2,4-triazole or 3 -a-T -ndecyl-4-phenyl-5-K ⁱ .ercapto-1,2,4-triazole;

In addition, 1,5-bimercapto-3j7-dipheiryl ~ / T, 2, ^ - triazolo-Zi, 2, a // _ 1,2,4 / - triaaol vev \\ can be ended.

(f) tetrazole; that can be substituted with 1 or snje Alkyl groups have 1 to 5 carbon atoms, a phonyl group a phenyl group substituted with a Benaaraia ™ grupi ^ e and / or an AUxylamidgruppe with 2 to 21 Carbon atoms, if desired;

709807/1041 _{0R! Q! NAL} inspected

like 5 ~ He.rcaptoteurazol, "i-Phönyl-ip-iuercaptotv- fcrazol, 1 ~ (m-Gaproamidplienyl) "-. 5-mercaptotetrazole, 1- (m-Lauroamiaphenyl) ~ 5-Biercaptotetrazole or 1 - (m «~ Beri2; aiaidp} ienyl) .- 5-mercaptotetrazole;

(g) oxazoles and benzoxazoles; which are substituted

can with Λ or two "alkyl groups with Λ to 5th carbon atoms, or phenyl groups, if desired,

such as 2-mercaptobenzoxazole;

(h) pyridines; which can be substituted with 1 or two carboxyl groups, or sulfo groups;

like li-mercaptopyi'idine-2,3-d "icarboxylic acid or l \ i-ilercaptopyridin-2 "sulfonic acid;

(i) - 'CMnoline, isoquinoline and 5 »8-dioxyquinoline; the

can be substituted with 1 or 2 carboxyl groups, if desired,

like 2-rlercaptoquinoline, 2-mercapto-isoquinoline, 3-Mercaptoquinoline-2,3 ~ dicarboxylic acid or 2-Her ~ eapto-5j8-dioxyquinoline;

(.1) pyrimidine; which can be substituted with 1 or

more alkyl groups with 1 to 5 carbon atoms, and / or 0: ro-. groups, if desired.

709807/1 041 originally inspected

such as S-mercaptopyrimicin, 2 ~ kercapto ~ 4 - "- iaetuyl - 6 - oxopyrimidine ,. Thiobarbitursau.ro or 2-lthylthio ·· 4- = isethyl-6-oxopyririidine;

with a benzoyl group (ic) morphiolin; the \ can be substituted _$ provided

desired;

vjie 2-mercaptomorpliolin or 2 ~ Me: r? capl; o ™ n- ~ th% oyi morpholiii;

(1) purine and caffeine;

vrie 2-Merca.X "3topurine and 2-mercaptocaffeine;

(m) tetrazainds; that can be substituted with a Alkyl group with 1 to 3 carbon atoms or a hydroxy], group;

like 2-Plercapto - ^ - hydroxy-6-iaotIiyl-1,3ϊ 3? & ϊ 7-tGtrazainden;

The above-mentioned compounds (a) to (πι) without subatituents, such as -SH groups, = S groups or -SRG groups, v / whether R has the aforementioned meaning, can also be used according to the invention as an organic compound.

VIIIc selenium acids of the general formula

H (E = O ^, -. Alkyl, phenyl),

70 9807/1041

ORIGINAL INSPECTED

such as ethylselenic acid or bensoloelenic acid;

IX. Hot dyes and 3 drugs (the GI-Sr. Refers to the "Color Index", 3rd edition, The Society of Dyers and Colourists * Bradford, Yorkshire (

1". Azo dyes (those that contain a -N = K group)

acidic dyes, e.g.

NaO:

Orange II (CI 15510)

(2) acidic iron dyes, such as

OH OH

NaO ₃ S

Chrora blue black RC (CI 15705)

0 9 8 0 7/1041

ORIGINAL INSPECTED

(3) direct dyes, such as

H ₂ N OH

NaO ₃ S

SO ₃ Na • HO NH ₂

_rN 4i / ^ i \; M ^

X ^ aO ₃ S

SO ₃ Na

Direct blue BB (CI 22610)

(4) Metal complex salt substances such as

O ₂ H OH H ₂ O SO ₃ H

HO ₃ S

Palatine real blue GG-F (CI 14880)

(5) Basic dyes, such as

NH ₂

Chrysoidine. (CI 11270)

709807/10 41

(6) ■ acetate dyes,

O ₂ N - //

(7) vat azo dyes

(I) true color bases, such as

NH ₂

Real orange G-Base. (OI 37005)

(II) true color salts, such as

z +

CF ₃

-N-

II

ZnCJl i

Eciit orange salt ED (CI 37050)

709807/1041

(III) Naphthol: how

Naphthol AS (CI 37505)

(I?) Eapid real dye CH,

Eapid real scarlet EH (CI 4-69)

(V) Sapidgene dye

CF ₃

N = N-M

SO ₃ Na

CU

COONa

709807/1041

(8) pyrazolone dyes. (those that have the structure

H -N = N-C - C-)

• I I!

contain ^ how

NaO ₃ S - //

= NC - C-CH ₃

I il

CJl

Cl

SO ₃ Na

Xylene real yellow 2 G (CI 18965)

(9) stilbene dyes, (those that have the structure

M-N = N-)

SO ₃ H SOjH

included), like

709807/1041 '

C ₂ H ₅ O - //

CH - </ V ^{N =}

SO ₃ H SO ₃ H

Chrysopiienin G (CI 24895)

(10) Thiasol dyes (those that have the structure

included) ₅ like

CH ₃

HO Ci

NaO ₃ S

"SO ₃ Ns

Diamine Pink BD (CI 15075)

2. Anthraquinone dyes (those that have the structure

contain)

709807/104 1

(1) mordant dyes, e.g.

Alizarin (CI 58OOO)

(2) Acid mordant dyes, e.g.

0 OH

0 SO ₃ Na Alizarin Red S (CI 58OO5)

(3) Acid dyes, e.g.

0 NHCH3 Il

NH - // \\ - CH

SO Alizarin Astral B (CI

09807/1041

(A) Acetate dyes j ζ * B.

2634136

NHCH ₃

NHCHaCH2OH

Cellitone

- Real blue S ¹ ER (CI 61505)

Vat dyes

(I) anthraquinone dyes, e.g.

Indanthrene blue HSU (CI 69800)

70980771041

(II) anthrone dyes, e.g.

(CI 60010)

J. Indigoid dyes (those containing the structure -CO-C = G-CO-),

/ I I

(i) Indigoid dyes of the general formula

-OC ^ / NH- -HN ""

e.g.

CO-

Indigo (CI 73000)

(2) Thioindigoid dyes der. general formula

-OC ^ _ / S-

709807/10 41

e.g.

CH ₃

CJl

CO / S

C = C

s / \ c

CH ₃

(CI 73385)

4. Soluble vat dyes

(1) indigoid dyes, e.g.

NaO ₃ SO

. . I ^H

-SO ₃ Na

Indigodol 0 (CI 73002)

(2) Chemical dyes, e.g. OCH ₃ OCH ₃

0.

SO ₃ Na

Anthrasol green IB (CI 59826) 709807/1041

5. "Sulfur dyes, e.g.

CGI 531S5)

6. Carbonium dyes (those that have the structure -G- included),

(1 :) Diphenylmethane dyes (those _T which have the structure / "X / λ

"X = / ti -V = / '

included), e.g.

AN (CH ₃ ) ₂

fi

NH

C £

Auramine

(2)? Triphenylmethane dyes- (those that use the Site structure '

included), ζ. B,

(CH ₃ J ₂ N - //

_τ +

= Ν (CH ₃ J ₂

Oxalic acid salt

Halachite green (CI 42000)

N (CH ₃ ).

Crystal violet (CI 42555)

(3) xantlium dyes (those that have the structure

included), e.g.

7ö98077TQ4t

Ehodamine B (CI 45170)

(4) Acridium dyes, (those that have the structure

contain en) »e.g.

NH

NH ₂

NO:

NH;

PhospMn (GI 46045)

709807/1041:

2634136

7. Quinone imine dyes (those that have the structure

P = IT-

included.) _?

(1) Azine dyes (those that have the structure

contain), e.g.

C £

Safranin T (CI 5024-0)

(2) oxazine dyes (those that have the structure

included) _s e.g.

709807/1041

2034181

N (CH ₃ ) ₂

Keldora blue (CI 51175)

(3) Thiazine dyes (those> which the structure

CK

contains), ζ.B.

(CHs) -Z-N

N (CH ₃ ):

(CI 52015)

8. Phthalocyanine dyes (those that have the structure

N "

contain.

0 9 8 0 7/1041

ORIGINAL INSPECTED

S, - Other dyes

(A) Cyanine dyes (those that have the structure

contain)

(B) quinoline dyes, e.g.

Quinoline yellow (CI 4,000)

(C) ITi trof substances, e.g.

Naphthol yellow S

(D) nitroso dyes, e.g.

709807/1041

X. Spiropyran compounds

(D

, 3,3-iriiaethyl-6 '-nitro-spiro- (indoline-2,2'-benzo-d ^ -pyran)

(2)

3- (3 ~ sulfopropyl) ~ 5-chloro-6'-nitrospiro- (benzothiazoline-2,2 ' -benzo-cC-pyran)

(3)

CH ₃ CH ₃

Br NO ₂

1,3,3-Irimetb.yl-6 ', 8 · -dibromo-7 ^! -nitrospiro- (indoline-2,2'benzo-cC-pyran)

709807/1041

1,3 »3 ~ trimethyl-6 '-nitro-8' -metiioxyspiro- (indoline-2-2 '■ benz ο -Jrpy

-S. ethyl ~ 6 '-nitro spiro- ("benzothiazolin- 2-2' -" benzo-X-pyran)

CH ₃

1,3 »3-Trimethyl-6 '-bromspiro- (indoline ~ 2-2' -benzo-C-pyr an)

709807/1041

CH ₃

1,5,3-Trimeth7l-6 -, 8 '-dibromspiro- (indoline-2-2' -benzo-c6-pyran)

NO ₂

I-ethyl-6'-nitro spiro- (naphtho - / 2,1-d7tiiiazolin-2-2 '■ b en ζ ο-jC-pyr an)

CH ₃ ^ CH ₃

CH ₃

1,3,3-trimethyl-6 ', 8' -dicilorspiro- (indoline-2-2 '■ benzo-i ^ iyran)

709807/1041

(10)

CH ₃ CH ₂

1,5- Dinietnyl-J-benzyl-e '-nitrospiro- (indoline-2-2' benzo-X-pyi-aa)

NO ₂

-6'-nitrospiro- (benzoselenazoline-2-2'-

b enzo-jj-pyran)

CH ₃ CH ₃

NO ₂

-8'-nitrospiro- (indoline-2-2'-

benzo- ^ T-pyran)

709807/1041

3-ethyl ~ 6 -bromspiro- (naph.tho-Z2,1-cJ7-thiazolin-2-2 benzo - i ~~ pyran)

OCH

-N 0- < XVMO ₂ (CH ₂ ) ^ SO ₃ H

lin-2-2 ^f -benzo-X-pyran /

(15)

CH ₃ / CH ₃

NO ₂

CH

1,3,3-Trimetiiyl-6 ^r -nitro-8 '-bromspiro- (indoline-2-2' -

709807/1041

(16)

Br NO 2 (CH ₂ KSO ₂ H

3- (4 ~ sulfobutyl) -5-2ietliO2y-6% 8 ^{ -aibromo-7 '-nitrospiro-zbenzo selenazoline-2-2' -benzo- ^ T-pyran /

(17)

3_ (3-sulfopropyl) -5-methoxy-6 ^t -nitrospiro-zbenzoselenazoline-2,2'-benz oX-pyran /

(18)

ο -H y-N0 ₂

_(CH2) 3SO3H

3- (3-sulfopropyl) -6 '-nitro spiro- (naphtho- / ?, 2-_d7-thiazolin-2-2 -Benzo - ^ '- pyran)

7098O7 / 1041

2634T9B

TF © irfe> Siit <iiäaiEgieiL · VUiJ-,

«© KP» W, - H8B »((eL (P)) ((&))" P)? g £))> gSJ O)) τ

2634I

. Methylene Blue ^ Crystal Violet and Ehodamine B from YTTTF. especially preferred.

Above are the materials used according to the invention described in detail. The following are now the; Stratification risks of the invention, in which · the) vQirrgeiüaaam tem h materials are used no

ErfisdongsgeiaäB are (A.) the inorganic material; (&)> the metal or the metal compound and (C) the organdiseiie ¥ @ rbindtag on dent iteäger · scr provided that these EanrgoiEieaiifeni · are · in · contact · with each other. Therefore kaaan mam. these; nenten as a respective layer thereof on the r üErsög ^ r sefeem. It is erfcirderilLiciBo ,; that ^: yourself; mindesifeesis edise? the / poiieMfeem is not located in SchieiLirfomm, "d" h "im! more detailed ,, fineear ^, punctiform; ' Particles: from e ^ fetfa 30 · Sl to about. o> ßw} - on the enager 'or' aiiGf äjm. others

L, fixes aimff dent carrier * as in is located.

The prop. 1 to 5 pointers trade fire; FlachdrMefeplatteii: - the, in whomi the IiLcMempf 'Ϊ Έ & I f ehe Sehi.cht aus- one

HateriaüL ,, eaiMera metal and / or a ¹ Efetrallver-

and. an organdisxsiQen VerMminCTg · consists of:

1 shows the. Ziistaaai. ^ Ma » the inorganic

• and / o & ei? ' the Ifefeallveirbinduaag and the orgaaaLse Yer-Mndtmg physically: nriLteabsBander are mixed. In this ff & JI means the asdriBsife " ^: sistand _r . In which the components ih ^ sifcaliscit are connected with each other" not the state ^ Each of the Eomponenten has its own film (or layer) · Ml and the layers thus formed over uniform j but, üjqxl ConditionE ^ τκ ©> at

each of the components is discontinuous, island-like particles forms, and these three kinds of shine with one another overlap and thus form the photosensitive layer on the support. The formation of such a state enables it to achieve the objects of the invention.

Iig. Fig. 2 shows an embodiment of the photosensitive layer of the invention in which any of the components, namely the inorganic material, the metal and / or the metal compound. and the organic compound forms a layer on the support and the other components are in the state of being physically mixed with each other, thus forming the entire photosensitive layer. In those embodiments where a layer is used, the preferred layer thickness is from about JOO Ά to about 10 u. 5/3

Jig. 5 describes an embodiment of the photosensitive Layer of the invention, in which any two of the components inorganic material, metal and / or metal compound (considered as a component), and organic compound on the support are in the state that they are physically related to each other are mixed, and is located on the layer thus formed a layer is formed from the remaining component, thereby forming the entire photosensitive layer. '

As is evident from the vorgen to nth description, are located at each of the aforementioned Au arbitrary. Guide shapes the inorganic material, the metal and / or the metal compound and the organic compound on the support in such a state that they are in contact with each other.

7Q9807 / 1 0 4 1

Specifically, the photosensitive layer of the structure shown in Fig. 1 is possible in one type, the photosensitive Layer of in Pig. 2, three types of structures are possible, since any of the three components are inorganic Material, metal and / or metal compound and organic compound is formed as a layer on the carrier, and the others are provided on the layer in the state in which they are physically mixed with each other, and the light-sensitive layer of the structure shown in Pig. 3 is possible in three types. So seven combinations are possible.

Next, the formation of the photosensitive layer of the non-treatment planographic printing plate of the invention is below "Use of four types of materials, two of them from a group of inorganic material, metal or metal compound and organic compound, and the others selected from the other two groups.

The Pig. 4 to 14 describe possible layer structures »Pig. shows the state where four kinds of materials are mixed together with the same structure as in Pig. 1 shown, acts. The photosensitive layer of this structure is possible in three types.

Pig. 5 describes an embodiment of the photosensitive Layer of the invention in which one of the four materials is layered on the support and the other three Materials on the layer are in the state that they are physically mixed with one another. This structure type is possible in twelve types, as it is possible in four types depending on the combination of the materials to be used is, and, moreover, there are three types in which two. Materials that fall into the same group from the three

709807/1041

Groups of inorganic material, metal or metal compound and organic compound can be selected.

6 shows the inversion of the layer structure shown in FIG. 5, in the three materials on the carrier in the state are provided that they are mixed together, and that .remaining one material is on top of it as a layer. This structure is possible in twelve types, as in the case of Fig.

Fig. 7 shows an embodiment of the photosensitive layer of the invention in which two types of materials are on the support are provided in the state that they are mixed with each other; a different material is as a layer on the so produced Layer is provided and the remainder is a material connected to it or absorbed thereon in the state of discontinuous island-like particles, so that there is no complete Layer forms, or there is the reverse case, in which a material on the carrier in the state of discontinuous Island-like particles is provided so that it does not form a continuous layer, another material is located as a layer on top of it, and the remaining two materials are provided on the layer in the state that they are physically are mixed together. This structure type is possible in 36 types.

Figures 8 through 12 describe structures in which two "the four materials form complete layers.

Fig. 8 describes the structure in which there are two types of materials are on the support as full layers, and the other two materials are then in the condition seen are "that they are mixed together. This structure

709807/1041

is possible in eighteen types.

9 describes the reversed case of Fig. 8, the carrier are provided in the state in which two · Endangered Species of materials on _t, that they are mixed together and the remaining two kinds of materials are then provided as full layers. This structure is possible in eighteen types, as in Pig. 8th.

Pig. 10 describes the structure in which one type of material is connected to the carrier in the state of discontinuous island-like particles so that it is not complete. layer forms; another material is on this as complete Shift provided. Another material is then provided in the state of discontinuous island-like particles so that it does not form a complete layer, and the remaining one material is provided in such a way that it is a complete Layer forms. This type of structure is possible in 36 types.

Pig. 11 describes the reverse structure of Pig. 10, in the one Material is provided on the carrier as a layer, another material is then in the state of discontinuous island-like Particle is provided so that it does not form a complete layer, another material is provided as a layer on top is, and the last material thereupon in the state of discontinuous island-like particles are provided so that there are -none forms complete layer. This structure type is in 36 types possible, as in Pig. 10.

Pig. 12 describes the structure in which a material is placed on the Carrier is provided as a layer, the other two materials are provided on it in the state that they are physically with-

709807/1041

are mixed together, and the last material on it as Layer is provided. This type of structure is possible in 36 types.

The Pig. 13 and 14- describe the structures in which three of the four materials are formed as layers.

Fig. 13 describes the structure in which two materials the support are provided as complete layers, another material on top of it in the state of discontinuous island-like Particle is provided so that it does not form a complete layer, and the last material on top of it as a layer is provided. This type of structure is possible in 36 types.

"Fig. 14 describes the inverse structure of Fig. 13 in which one material is provided on the support as a layer, another material is provided thereon in the state of discontinuous island-like particles so as not to be complete Layer, and the remaining two! Materials on top are intended as full shifts. This type of structure is possible in 36 types, as in FIG. 13.

As described in detail above, the structure is photosensitive layer of the invention, in which the inorganic material, the metal and / or the metal compound and at least one organic compound capable of impairing the mutual reaction on the support in the state are provided that they come into contact with each other, possible in a number of types. For example, if a material is made of Each of the groups will be selected, the three materials provided in the structures shown in Figs. These Structures are possible in seven types. If on the other hand

709807/1041

two materials are selected from one group and the other two materials are each selected from the other two groups they are in those shown in FIGS. 4 to 14 Structures provided. These structures are of 279 types possible. Of course, the types of material selected are not limited to the three or four mentioned above, and sometimes five or more materials can be used to achieve the objects of the invention. In this Case, the number of possible structures is increased considerably.

In the above description, the term "physical" in the passage "the state that they are physically mixed with one another or are in a mixture with one another" the fact that constituents are not positively subjected to a chemical reaction, and thus it must be recorded, that the presence of a product due to physical absorption, chemical absorption or an only partial chemical reaction is to be expected.

The "state that the ingredients are physically mixed with each other" means that the ingredients form discontinuous island-like particles (microscopic), and these particles with each other in ^eru ^ ^ung ^>% ι% ^η "pass the conditions necessary for the formation of such a surface condition generally that two or more kinds of materials should not form individual complete layers but should always be in the state of discontinuous island-like particles thus two components

709807/1041

"in the state of a physically commingled state" are in a layer of another component, these are three components "in the state of mutual overlap" as described above. Even if two materials are used as Layers are provided *, and the other material between the layers in the state of discontinuous island-like particles is provided so that it does not form a complete layer, these three materials are in such a state - that they have contact areas according to the invention.

According to the invention, therefore, the formation of the state of discontinuous island-like particles and the contact state of each component are important considerations.

The formation of the state of discontinuous island-like particles is achieved, for example, by vapor deposition. According to this Method, a mesh screen is placed over the vapor deposition surface, and a material is evaporated in a vacuum so that the material is in the state of discontinuous island-like particles. Then a material is applied to the vapor-deposited material Mesh screen is placed, and another material is vacuumed vapor deposited so as to be in the state of discontinuous island-like particles, the foregoing two materials are generated in the state that they are mixed with each other. Of course, it should be used for vapor deposition of the second material, the superposition of the mesh screen can be controlled so that areas arise in which the second Material is suitably overlaid on the first material, i.e. the mesh screen should not be overlaid in such a manner \ O. all of the second material to be evaporated on the already vapor-deposited first material adheres, and you should control so that the second material not only on the vapor un soberflache that has been subjected to exposure,

7 09807/1041

without being covered with the first material. .

This discontinuous state can be achieved by placing a mesh screen on the carrier first material is vapor-deposited, then the mesh screen is placed on the carrier with a slightly offset position, and the second material vaporized, since the mesh screen is hardly placed in exactly the same place as for the first vaporization.

Mesh screens with different distances or openings can be used where the first and second material are vapor-deposited The element to be overlaid does not always have to be one with the regular openings owns like a mesh screen; one can rather use a mask in which irregular openings are arranged irregularly, e.g. use a pattern from a grained sieve. However, if any or all of the components inorganic material, metal or metal compound and organic compound are evaporated according to the aforementioned method it is impossible to make the resolution larger than the aperture distance of the mask. It is therefore necessary use a mask with very small openings or very small spaces, up to 0.15 mm (100 mesh), and the use of such a mask suffers from various limitations.

As described above, the use of a MasTce necessarily limited by their resolving power, and to increase the resolving power it is necessary each of the components in the island-shaped pattern (consisting from the island-like particles) to be deposited at a finer distance. As a result of various attempts in this matter has been found that vapor deposition in a certain amount

709807/1041

formation of an island pattern with a fine pitch, whereby it is possible to create a very efficient state of discontinuous island-like particles.

The following statements relate to the conditions to create an island-like discontinuous state. To keep the three components in contact with each other, at least one of these components must be in the state of a discontinuous island-like pattern (must be insufficient in thickness to form a film), e.g.

the components deposited with an average thickness of 10 α

2 (in other words, a deposition amount of ip µg / cm), these components are in contact with each other. on the other hand can, e.g. with a thickness of 10 Ai or more, components form a film, and these components are located

then

\ not in contact. The mechanism of vacuum evaporation is very complicated and not well known * According to electron microscopy The growth of vaporized substances could sometimes follow the following stages: (1) formation and growth of germs; (2) aggregation of the particles; and (J) repeated aggregation forming a coherent film. In particular have Experiments reported on the vapor deposition of gold films, that the particle density increases until the amount evaporated becomes 0.6 µg / cm, and then the particle density decreases exponentially. This can be explained if the formation of nuclei predominates until the amount evaporated is about 0.6 µg / cm according to which the aggregation predominates. Furthermore, the particle sizes are in a Gaussian distribution, whereby'die Particle size increases with increasing amount. The maximum particle size in a thin gold film that is in a lot . of 1.0 µg / cm is reported to be 60 to 80 &. Furthermore, it was observed, that until reaching a deposition amount of about 6 ng / cm the particle size

709807/1 OA 1

ο distribution is quite even, but at about 20 ug / cm the particle shape is extremely irregular and .the In- ■ the number of elongated particles increases, the length of such particles being from 2000 to 3000 i. The electric continues to fall Resistance of a thin film of gold, copper or aluminum drops sharply at 32 to 3 ^ pg / cm. It follows that there are many bridges are formed in the island-like deposits just at this point in time. The relationship between the separated The amount and the island-like shape depends on the type, shape and temperature the underlying substance, gases adsorbed on the underlying substance, the yaknum quality in vapor deposition and the yakuum evaporation rate and the evaporation rate, respectively away. However, it is found that when the deposition is low of less than 8 ug / cm, the evaporation in an island-like state and, up to 3 ^ - jag / cm, in the level of Eoalescence of island-like deposits and, up to 50 µg / cm the vapor deposition in a mesh-like or net-like form and,

when the deposition amount exceeds 80 ng / cm, in the form of a contiguous film (layer) takes place.

The above description is only applicable to the case, where a reasonably smooth surface is used, and it is believed that in the case of a surface with irregularities of over 1 u, e.g. a surface roughened with sand, a very different behavior takes place. In the case of the island-like, discontinuous film required according to the invention, however, it is clear that even a

vaporization with a deposition amount of less than about 60 / Ug / cin The vapor deposited film obtained has sufficient performance properties and the resolving power is increased.

When the deposits in a discontinuous island-like State, i.e. not as a uniform film, is present

709807/1041

a definition with a thickness meaningless «Therefore poses in such a state, the deposition amount Gug / cm. ) a better parameters for definition. On the other hand, with a sufficiently large deposit amount to form a uniform layer the * thickness (S.) used for definition will. It is difficult to give a clear minimum thickness that is required to achieve a uniform layer. According to the invention, j is, however, this minimum thickness generally about 500 §. . -

The following are the amounts of components ((A) inorganic Material, (B) at least one metal or metal compound., and (C) organic compound) indicated "

In the presence of a pressure plate as in Fig. 1, it is required that the deposition of (A), (B) and (G) be in a comical state, and each component should have a thickness of less than 300%. Preferred deposition amounts are from 0.1 to Ojag i / em ² for (A), from 0.03 to 30 jig / em ² is (B), and 0.1 to 3 9g / cm for (G). _: . ■ "

When the Flachdruckpiatte a construction as shown in Fig. 2 or Fig. 3 has _$ it is necessary that one component is deposited in a filmahnlichen state, so that the bead here is 300 §. to 10 ii. The other two components have a thickness and amount as described above for Mg. 1. Furthermore, although not shown, can

' W-

The creation of a roof rack plate can be realized, which has a structure made up of two layers of the two components and one that is discontinuous. has an island-like state. In this case the layers each have a thickness of % to 10 p * and the other is less than 30 p. Thick.

■ 709807/1041

In the planographic printing plate with the structure of Fig. 4- to 14- possesses a layer-like deposit 300 2 thick. to 10 ii, and the discontinuous island-like particulate Material has a thickness of less than JOO 2 ..

Preferably the components (A) are inorganic material components, (B) metal or metal compound, and component (C) organic compounds in a ratio of 100: 1 to 300: 0.3 to 30 by weight used.

Well known methods of making thin films are, in addition to vacuum evaporation, sputtering (Sputtering) ion plating, electrophoretic deposition, Gas phase separation, spraying, and the like Methods known. The aforementioned methods are in "Handbook of Thin Film Technology" (editors L.I. Meissel and E. Glang) described. It goes without saying that any of the foregoing methods can be used provided the foregoing Embodiment is achieved.

The methods of sputtering and ion plating are similar to vacuum evaporation and are particularly suitable for manufacture of the planographic printing plate material of the invention. For the deposition of a metal or a metal compound is mainly used Direct current atomization is used, and for the deposition of a germanium and sulfur-containing mass is preferred AC atomization application.

Applying the vacuum deposition for producing a ElaehdruckpAatfee the inorganic material, the metal or metal compound and the organic compound are respectively heated and thereby deposited by dissolution or sublimation, for example at 4-50 to 600 ⁰ C for a Ge-S-mass and 250

709807/1041

up to 29O ° C for a 2-mercapto-5-lauroamidobenzimidazole as organic Link. The vacuum deposition rate is preferably 1 to 50 2 / sec.

For the Tall * that the aforementioned steaming method is used is used to form the state of discontinuous island-like particles and a layer of an organic Material are those organic materials that can be vapor deposited without thermal dissociation, and limited other organic materials can be created in the state of discontinuous island-like particles, ornaments by immersion the support, or the support on which a material has already been deposited, into a solution that has been prepared is by dissolving the organic material in a solvent. The amount of deposition can be determined by controlling the concentration of the solution. As a solvent you can e.g. water, methanol, ethanol or propanol can be used. The concentration is, for example, 0.01 to 0.2 percent by weight. Of course, it is also possible to use the inorganic material or the metal or the metal compound on one Separate solution from this. For example, if silver is used as the metal, good results are achieved by immersing it in a solution of silver nitrate, silver acetate, silver sulfate, etc., in Water, alcohols and the like. Obtained. In the jail of copper find preferred types e.g. copper nitrate, copper acetate and copper sulfate Use. When using the aforementioned immersion method for the other metals, metal salts of Sulfuric acid is used. Preferred concentrations of the solutions thereof are in the range from 0.05 to 2 percent by weight, The immersion takes place, for example, for a period of 10 seconds to 2 minutes at tree temperature, and the immersion solution has

9807/1041

preferably a temperature of 10 to 40 ⁰ C. In Pail of using an aqueous solution of these, one can immerse a few hours in an alcohol after the deposition of the metal, to facilitate uniform drying.

The treatment-free lithographic printing plate of the invention, which is obtained in the aforementioned manner, can be mounted in a printing machine and immediately after exposure to Pressure can be used.

A comparison of the planographic printing plate made using the mass in which an organic compound according to the invention is used, with a planographic printing plate, in which the organic compound is not used, makes it clear that the printing plate of the invention has a distinctive character Difference between hydrophilic and oleophilic areas on the surface and their printing surface is free from contamination. The printing plate obtained by adding the compound of the present invention possesses an excellent plate surface because of the large difference between its hydrophilicity and oleophilicity, while the printing plate obtained without the organic material has a dirty plate surface the slight difference between their hydrophilicity and Possesses oleophilicity. Moreover, the planographic printing plate of the invention has various properties, e.g. Printing ability of the printing surface is very stable, and its printing resistance is excellent such that, for example, several tens of thousands Prints or copies can be made. Thus, the invention has great practical value.

The examples illustrate the invention. In the following examples, when (A) the organic material, (B) at least one

709807/1041

Metal or a metal compound and (C) the organic Compound used in an amount in excess of 10, 30 and 3 µg / cm, respectively each component is in Jfilm form, and if the application takes place in less than the specified amounts, each component is in the island-like discontinuous State before.

example 1

ELn inorganic material with the composition Ge-S ₀ , - (here and in the following the numerical value indicates the ratio of the atomic numbers) is produced by melting germanium with a purity of 99.999 % and sulfur in a vacuum as well as rapid cooling. 150 mg of this inorganic material as an evaporation source are placed in an aluminum oxide-lined tungsten basket, which is placed in a vacuum deposition device. Then an aluminum plate measuring 300 × 400 mm, which has been roughened with sand and subjected to anodic oxidation in an amount of 2.4 g / m in 20% strength by weight sulfuric acid solution in water at 25 ° C. bent so that it has a slight curvature ·. ,, and arranged in the vacuum evaporation device at a distance of about 30 cm from the aforementioned evaporation source. The device is evacuated to a vacuum of 5 x 10 Torr, and then the aforementioned inorganic material is evaporated until the deposited. Quantity reached 15 Ug / cm. Then, in the same way as described above, 20 mg of i-phenyl-5-mercaptotetrazo-1 are added to the aforementioned basket and evaporated until the deposited amount reaches 0.6 μg / cm. Then, 100 mg of silver are a Oneness of 99 "99 ° / ° i ⁿ where the aforementioned basket and evaporated until the deposited amount 6.0 ^ üg / cm reaches" This results in a treatment-free according to the invention. ! Planographic printing plate. In this case, the aforementioned deposition

709807/1041

amount determined by reading the value from a monitor (DTM-200 monitor, manufacturer Sloan Co., U.S.A), with connected to the vacuum evaporation device. The same goes for for the following examples and comparative examples.

A positive exposure mask is then placed on the vapor-deposited surface of this element, which is then used for a duration of 1.5 minutes using an exposure device (PS-Light) with an output power of 2 KW (manufacturer Euji ^ Öm Co., Ltd.), hereinafter referred to as "PS light", is subjected to exposure. A sharp positive image is obtained here. This element is then put into a planographic printing machine vom lyp 600 CD (HamadePstar 600 CD, manufacturer Hainada Printing Machine Co.), hereinafter referred to as "600 CD", without any other treatment. Thereupon is wetting water, as it is used in conventional planographic printing, applied to the image surface. After that When the printing ink is applied to this, a positively colored planographic printing plate is obtained. Using this pressure plate 2000 prints or copies are printed.

For comparison, a planographic printing plate is produced in the same way, but with the vacuum deposition of the 1-phenyl-5-mercaptotetrazole is omitted. The comparison sample has considerably poorer values with regard to the oleophilic or color-absorbing properties, and there can be no sharp picture obtained even when using the same printing process, as described above.

It can thus be seen that the sample of Example 1, compared to the comparative sample, a marked difference between hydrophilic and oleophilic areas, and still good printing properties and a sufficiently increased sensitivity

709807/1041

opportunity possesses. - 63 -

Unless otherwise stated, in the following examples all process conditions and product properties, e.g. deposition conditions, exposure and printing or copying conditions _{f are} as in example 1. ·

Examples 2 to 25

In the same manner as described in Example 1, a planographic printing plate material is produced by vacuum deposition on an aluminum plate, which has been subjected to sand roughening and anodic oxidation, as described in Example 1, of an inorganic material of the composition GeS ^ π with a deposition amount of 15 / ig / cm at a vacuum of 5 x ΊΟ "x ⁷ Torr, the organic compound Ca") according to Table I in the deposition amount (b) according to Table I, and of silver with a deposition amount of 6.0 µg / cm this The lithographic printing plate material is exposed using PS light for the time t indicated in Table I and then mounted in a printing machine without any further treatment. After treatment with wetting water and inking, which are customary planographic printing processes, a positively colored planographic printing plate is obtained. When printing with this printing plate, 500 sheets of paper can be obtained in each case.

7 0 9807/1041

Table I.

At sv ± el

Organic compound Ca; .

1- (mC aproamidophenyl) -5-mercaptotetrazole C ₅ H ₁₁ CONH ^ .NC-SH

N N

l-Phenyl-5-mercaptotetrazole C ₆ H ₅ -N - C-SH N. N Deposition amount

(b)

0.6

Exposure time (t) (min)

3-methyl-4-phenyl-5-mercapto-1,2,4-triazole> C ₆ H ₅ -N - C-SH

I H ■

/ ^C v ^N

CH 3 "^ ir" 1.2

CH ₃ -N - C-SH

I Π

CH ₃ N · cn

GO

O)

example
6th

Organic connection

'3- (p-CGproaraidophenyl) -4-ethyl-5-mercapto-1,2, 4-trlazolv C ₂ Hs-N - C-SH

3-n-Undecyl-4-phenyl-5-mercapto-1,2,4-triazole \ C ₆ H ₅ -N - S-SH

■! P.

^ ^c v ^N

Amount of separation

(b)

(yg / cm2) 0 _f 5

0.3

Exposure

1,5-di-mercapto-3,7-diphenyl [1,2,4] triazolo- [1,2, a] [1,2,4] triazole.

C ₅ H ₅ ,

N '

Il

SH-C

'N - C-SH

I H

N, Ν

U)

CD

example

Organic compound '(a)

l-phenyl-2-mercaptoimldazole

C ₆ H ₅ -N - C-SH I II

Deposition amount

(b)

0.6

Exposure time (t) (min)

CO OO O

10

2-hexadecylthioimidazoline hydrobromide

N = CSC ^ ₆ H ₃₃ -HBr

.NH .1,2

11

2-thioxo-4-oxothiazoline

H-N-C = S

ι ι ·

.C S -

H ₂

B ^ ispiel '12

Organic compound (a)

2,5-dimercapto-1,3,4-thiazole

Deposition amount

(yg / cm ² )

Exposure time (t)

(min)

O CD Op O

13th

14th

15th

HS Λ S SH ßismuthiol II N - N-C6H5

Ii i

2-Ethylthio-4-methyl-6-hydroxypyrimidine ^. CH ₃ , ^ OH

V ^N '

SC ₂ H ₅ 2-f1ercapto-4-hydroxy-6-methylρyriraidin ■.

HO

CH ₃

N. · N

SH ¹ J ²

0 _? 6th

CO

CD

Example"

16

.Organic connection (a) "

N, N, N ', N'-Tetramethyl-4,4'-diamino thiobenzophenone · CH ₃ ^ _Γ -, r-Λ / CH ₃ CH ₃ Vz / | I Vr- / "^ CH ₃

Deposition amount
' (b) (Vig / cm ² )

Exposure time (t)

(min)

οο ο -α

17th

18th

19th

20th

Sodium diethyl dithiocarbamate '

N-C

C ₂ Hs

Silver diethyl diethyl carbamate C ₂ H ₅

N-C

C ₂ H ₅

N, N, N ', N'-tetramethyl-p-phenylenediamine hydrochloride

^ λ-λ / CH ₃

N - // ^N ) -N CH ₃ VZV ^ CH ₃

Monoethyl urea C ₂ H ₅ NHCONH ₂ 0.5

0 _T 2

l _f 0

(Ti oo

example

21

22nd

23

Organic compound (a)

Bimethylolurea

(HOCH ₂ NH) ₂ CS A-Phenylthiosemicarbazide

H ₂ N -NH-C-NH-C ₆ H ₅ II S

2,5-di- (I, l-dimethylbutyl) hydroquinone C ₃ H ₇ -C (CHa) ₂ • OH

, Deposition. lot

. (b)
. . (yg / cm ² )

1.1

0.9

0.6

■ exposure time (')

(min)

(CHs) ₂ CC ₃ H ₇ ISJ

CD

to

CD

As a comparative example to each of the above examples, a comparative example is made in the same manner as above described, performed, but the vacuum deposition the organizational connection is not carried out. At the When printing, each sample is colored negative. When assessing the printing process, i.e. the distribution behavior of the Printing ink, it is found that the oleophilic properties of the image areas are poor.

If in each example the sample is compared with the comparison sample with regard to the printing properties, it can be seen that that the organic compound of the invention improves the distribution of the printing ink on the printing plate, prints with Gives excellent quality images and increases sensitivity. In particular, it is under practical From a historical point of view, it is surprising that the type of printing plate changes, that is, the comparative sample is of the negative type, while the sample of the present invention in which the organic compound has been used is of the positive type.

Examples 24 to 27

In the same way as in Example 1, a planographic printing plate according to the invention is produced, in this case, as can be seen from Table II, the composition and amount of deposition the inorganic material, the type and amount of deposition of the organic compound, as well as the type and amount of deposition of the metal changed. This planographic printing plate is made by means of. Exposed to PS light for the duration shown in Table II. When carrying out the aforementioned printing processes, a positive planographic printing plate is obtained with which 500 to Ί000 sheets of paper can be used can be printed.

709 8 0 7/1041

'■■■■', ■ -;. \ ' Table II ,

:, ■ '■■'. '■' ■ ■ '■' ■■ ■, '■. Number·

■. ■ "■ '. · · ,. ■''. ■ · ■■' ■ ^: '■' ■ '■', ''. 'Der ge'

'Inorgani-',. ■. ■ '. '■.' Printed

see comparison _{Men e} ". '· ■■ ■' ■ ■■ ···· ·. ■.. 'tungs- arches

Example , Binding ^& “Organic Connection. "'. · .Henge · Metal oil, quantity duration.

: ',' ■■■ (yg / cm ² ) ■. '■■■

(Ug / cm ² )

. (jig / cm ² ) (min)

24 GeS ₁ J ₇ 11 2- | - \ ercaptobenzothiazbl

2 _; 4 Ag V 6.0

25 ■ GeS.2,5 15

26 '". GeS ₂ , 5 12.5 2-Hercaptobenzoimidazole

NH

C-SH

^ v

27 ■ GeS _2/5 '15 l-phenyl-5-mercaptote.trazol

0.5

Ag

6.8

2-Hercapto-6-methylbenzotiiiazole 0.8 Ag 6.

■ · ■ · '■

CBs

6.0

In 6 _? 0

1,000

500

500 l

fs?

σ) co

σ>

On the other hand, a planographic printing plate material was used as a comparative sample in each example in the same manner as above described, prepared, but the evaporation of the organic compound is not carried out. While printing With this printing plate material, the oleophilic properties of the image areas are shown, that it is colored negatively are poor, and the image quality of the prints obtained therewith is also poor. Changed in these examples the addition of the organic compound changes the printing plate from negative type to positive type and, moreover, the image quality the printing surface is greatly improved.

Examples 28 and 29

A planographic printing plate material of the invention is prepared in the same manner as in Example 1. In this pail will be as can be seen from Table III, the composition and amount of the inorganic material, the kind and amount of the organic compound as well as the type and amount of metal changed. Every planographic printing plate material is exposed to PS light for subjected to the duration indicated in Table III. Using the same printing procedures as described above, obtained an ITegative printing plate and 500 sheets of paper are obtained.

709807/1041

• inorganic

B eJ ₇ SpJeI see connection - amount connection (yg / cm ² )

28

29

GeS ^

GeS ₂ , s

15th

15th

Table III Organic Ve-rT-ri.-prh '^ g ;.

• l- (m-caproamidophenyl) -5-mercaptotetrazole

C ₅ Hn CONH '

N - C-SH

I J

V "

2-ΜεΓθ3ρίο-5-ΐ3υΓθζο ± πι1α3Ζο1 '

.CiiHisCONH

C-SH

NH

(yg / cin ² )

β-. ΗθΦαΙΙ -

Oj 6

Ag

Ag

(yg / cm ² )

v °

Exposure time (min)

■ -si

VM I.

N)

CD CO

CO CD

For comparison with the samples of this example, samples are prepared which do not contain any organic compound. There · if these samples have a negative coloration, no change occurs for the plate type. However, the prints obtained have inferior image quality.

Examples $ 0 to 58

In the same manner as in Example 1, on an aluminum plate which has been subjected to sand-roughening and anodic oxidation as in Example 1, the inorganic material at a vacuum of 5 x 10 ^y Torr, and then the organic compound, and further evaporated the metal or metal compound. The composition of the inorganic material, the type of organic compound and the type of metal or metal compound are shown in Table IV. In this way, a planographic printing plate according to the invention is obtained. This planographic printing plate is subjected to exposure by means of PS light for the duration indicated in Table IV and then, without further treatment, mounted in a planographic printing machine. By carrying out the conventional planographic printing processes, treatment with wetting water and application of printing ink, positively or negatively colored planographic printing plates are obtained. When printing using this printing plate, the copy counts shown in Table IV are achieved.

709807 / 1Ό41

Table IV *)

3eisp ielMajterial lot Organic connection lot Metal amount (yg / cm ² ) Belichr.
duration ." Plat
ten-;
Type'',
(P; N * number of
. printed
Sheets
*> ■, ■. I. ISJ
"CD
Oe) . (jig / cm ² ) (yg / cm ² ) 6.0 (min) <P 30th GeS ₂ 15th l-phenyl-5-mercaptotetrazole, Oj6 Ag 0.2 . 1 P. • ι όοο 31 'Ge ₃ SS ₆ OPs 13th N-phenyl-3-naphthylamine 0.15 Ag O _f 85 8th P. 300 32 GeS ₂ , 5 15th 2-Hercapto-4-hydroxy-6-
me thy 1-1,3, say
tet razaind en
CHs' - ^ N ^, _, _T 1.0 AgJ ■ , 'n 300 ι I
j NH SH
OH

33 SnS2 24 l-phenyl-5-mercaptotetrazol '0.6 Ag 0.6 10 P' 500

*) The order of deposition is: inorganic material, organic compound and metal,

from the wearer

**) P = positive, N = negative

Then the order of the vapor deposition of the organic compound and the metal (or metal compound) is changed. The other operations are performed in the same manner as described above. The results are in
Table Y compiled.

709807/1041

Inorganic
see s
Material. lot metal lot table V • .Bei- ·
management
duration example (yg / cm *) (yg / cm ² ) organic connection lot (min) GeS 2 15th Ag 6.0 (yg / cm ² ) 2 34 Ge ₃ sS β oZn 5 15th Ag. '6.0 l-phenyl-S-mercaptotetrazole 0.6 2 35 l, 3,3 ^ trimethyl-6? -
nitrospiro (indollni-2,2'-
b enzo-a-pyran) • 2.0 CH ₃ .CH ₃

O CD QO O

"36.

37 38

*) The

GeS ₃ ,? GeS ₂ , 5

15th Ag; 3 0.85 15th Cu 10 3.0 Ag J ⁰ J ⁹

CH ₃

2-fyiercapto-A-hydroxy-6-methy1-1,3,3a, 7-tetrazaindem.

l-phenyl-S-mercaptotetrazole
l-phenyl-5-mercaptotetrazal

0 _f 5
0.17

3 »5

3.5

Plat-

ten-

Type

p
ρ

number of

printed sheets

1 000 500

500

500 500

The sequence of the deposition is: “Inorganic material, rmetal, organic. Material, from.

Carrier.

= Positive, N = negative

CO Oil

• -78- 2634198

For purposes of comparison with the samples from Examples 30 to 38 samples are produced that do not contain any organic compounds. None of these samples can be stained and used with it is impossible for these samples to perform printing.

Example 39

In the same way as in example 1, an inorganic material of the composition GeS ₀ , -

-5 '

evaporated at a vacuum of 5 x 10 torr until a

Deposition amount of 36 / µg / cm is reached. Afterward a sieve made of stainless steel (optical transmittance 28%) with a very small mesh opening (500 mesh) in intimate contact with the aforementioned vapor-deposited film. brought. The system is kept in a vacuum bath and then i-phenyl-5-mercaptotetrazole is evaporated by the aforementioned Stainless steel sieve on the aforesaid vapor-deposited film in a discontinuous state in vacuum

until the amount of deposition reaches 2.4 yug / cm. The aforesaid stainless steel screen is then removed, and then the stainless steel screen is placed again on the aforesaid evaporated film, whereupon Ag is deposited on the aforesaid evaporated film in a discontinuous state at a vacuum of 5 x ^/ ] 0 ~ ' ^? Toirr?

is evaporated until the deposition rate reaches 24 µg / cm. The thus obtained element is exposed to three minutes (by means of a jet-printer 2000), and then with water and wetting _ψ treated with color development, thereby obtaining a colored positive planographic printing plate.

70 9807/1041

As a comparison sample to the sample according to the invention a planographic printing plate prepared in the same way as described above, but with the attenuation the organic compound is omitted. With this printing plate, the color is not on the surface of the Plate distributed, and thus the plate is unsuitable for printing.

Examples 4-0 bis

In each of these examples, in the same manner as in Example 1, on an aluminum plate which has been subjected to roughening by means of sand and anodic oxidation, as in Example 1, the inorganic material having the composition shown in Table 6 at a vacuum of 5 x 10 "^ Torr. Then the organic compound and the metal or the metal compound according to Table 6 are evaporated in the amounts shown in Table 6, whereby an S ¹ lithographic printing plate according to the invention is obtained. This planographic printing plate is exposed to PS light for subjected to the period of time indicated in Table 6 and then, without any further treatment, mounted in a planographic printing machine. Using conventional planographic printing operations, treatment with fountain water and distributing ink, a positively colored planographic printing plate is obtained. Print runs reached.

709807/1041

Table VI

CD CO CO CD

example Inorganic
sches lot Organic connection lot metal lot Exposure
tion
duration Number
eggs ge
printed
Sheets • 40 GeS ₂ (yg / cm *) Hithizon . 0.2 Ag 5.0 (min)
2 . 500 41 GeS ₂ 4.5 Zinc diethyl thiocarbamate 0 _; 3 Ag. 5.0 2 500. 42 GeS _{2; 5} 3.0 1- fjvenyl-5-inercaptotetrazole- 0.9 AgJ 1.0 3.5 300 '43 GeS ₂ 4.5 Methylene blue 0.5 Ag 5.0 2 500 44 GeS ₂ 4.5 Crystal violet 0.8 • Ag 5.0 · 1 "500 45. GeS ₂ ■ 4.5 Behenic acid 1.0 Ag ⁵ J ⁰ Γ 500

Example 46

GeSo c is produced by melting Ge with a purity of 99 »999% and S in a vacuum and rapid cooling. 400 mg of the GeS £ c obtained are placed in a tungsten basket lined with aluminum oxide, which is arranged in a vacuum vapor deposition device. Then an aluminum plate measuring 300 χ 4-60 mm, which has been subjected to roughening by means of sand and anodic oxidation, is bent so that a slight curvature arises and then in the vacuum vapor deposition device at a distance of about 30 cm from the aforementioned Evaporation source arranged. The vacuum deposition is continued until the monitor, which is connected to the aforementioned device, shows a deposit amount of 36 / Ug / cm. The deposition thus obtained is in a 0.06 wt .-% solution (at room temperature, ie 22 ° C) of i-Phen.yl-5-mercaptotetrazole in ethanol immersed for a period of 15 seconds at room temperature (22 ⁰ C) dried and then immersed in a 0.5 wt .-% solution (at room temperature, ie 22 ° C) of silver nitrate in water for a period of 60 seconds, washed with water for 30 seconds and further in ethanol (at room temperature, ie 22 ⁰ C) immersed for a period of 3 seconds and dried. In this way, an S ¹ printing plate material according to the invention is obtained. A positive exposure mask is placed on this material, which is then exposed imagewise for a period of 2 minutes using a jet printer 2000 (exposure device, manufacturer Oak Manufacturing Co). A sharp positive image is obtained here. This plate is without jegli.che treatment, in a planographic printing press, 600 Cd, mounted and subjected to conventional treatment with Wasserben _e tzuns and color ^ nverteilung. A positively colored planographic printing plate is obtained here. With this planographic printing plate you can

709807/1041

Print 10,000 sheets of paper.

Examples 4-7 through 58

In these examples, as in Example 46, on an aluminum plate which has been subjected to roughening by means of sand and an anodic oxidation, an inorganic material of the composition GeS ₀ C at a vacuum of 5 ^χ 10 Torr deposited until the deposited amount of 36 / Ug / cm reached. This is followed by immersion in a 0.06% strength by weight solution (at tree temperature, ie 22 ° C.) of the organic compound according to Table 7 in ethanol for a period of 15 seconds and drying and then immersion in a 0.2% solution % Solution (at room temperature, ie 22 ° C) of silver nitrate in water, washing with water, immersion in ethanol and drying. A planographic printing plate according to the invention is obtained here. This plate is exposed to Jet Light 2000 for 1 minute and then subjected to the treatment with water wetting and distribution of color. A positively colored planographic printing plate is obtained here.

709807/1041

Anorga
niche lot • ■ Table YII 2634196 - C-SH
Il Example & l (yg / cm2) Organic link ^GeS 2 _; 5 .36 47 ! - (m-CGproamidophenyD-S-mercapCotetrazole
C ₅ H ₁₁ CONH - // Λ N
I.

48 "" 2-t \ ercaptobenzimidazole

49 "" 2-flercaptobenzothiazole

50 "." 2- "fKioxo-3- (m-methoxy phenyl) -4-methyl-A

1,3-thiazoline -

i Il

-N - C-CH ₃

51 "" 2-Thioxo-3- (3-nitrophenyl) -4-methyl-A ^lf -

1,3-thiazolite

, - C-CH ₃

I i!

• N-C-CH ₃

CH ₃ 53 l-pfjenyl-S-mercaptotetrazole

709807/1041

inorganic

Example Material Amount Organic Compound

(Mg / cm ² )

54 _GeS l.l'-Didodecyl ^^ '- tönylenMiipyridium

2 | 5 3d dibromide

^Xx CH = CH- / ^/ ^ N ⁺ -Ci ₀ H ₂ χ-2Br

"" Fatriuindiethyldithiocarbamat

C ₂ H ₅ ^ ^ .S

NC
C ₂ H ₅ &quot; ^ SNa

"" Dithizün

C ₆ H ₅ NHN = CN = NC ₆ H ₅

.SH. .

57 "·» Ν, Ν, Ν ', N'- |> tramethyl-4 _> 4 ^I -diaminothio-

benzophenone
ν. (Thiomichler's ketone)

CH ₃ ι ν ι y / CH ₃

^ V / NXV / \\ _ _n

CH ₃ \ /  \ y

5.8 »" ljS-Tt-imethyl-ö'-nitrospircKxndolin -2,2'-

benzo-a-pyran)

709807/1041

These planographic printing plates containing the organic compound of the invention contain, have improved properties and can be colored positive. Without these organic compounds, the improvements shown are not possible.

Examples 59 and 60

It is a planographic printing plate material in the same manner as in Example 46, except that the organic compound used in accordance with Table 8, and the concentration of the aqueous silver nitrate solution 0.06 wt -.% Is. When printing with these materials, each x) is colored positively; 700 to 1000 sheets of paper can be printed.

Table VIII

Organic connection

59 3- (p-caproamidophenyl) -4-ethyl-5-mercapto -1,2,4-triazole

60 '1- (m-Benzamidophenyl) -5-mercaptotetrazole

Examples 61 to

According to Example 46, the inorganic material according to Table IX is evaporated on a sand-roughened aluminum plate at a vacuum of 5 × 10 -5 Torr until the deposited amount reaches the value given in Table IX. Subsequently, the aluminum plate in a 0.06 wt .-% solution (ie Saumtemperatur 22 ⁰ C) is immersed in Table IX signed ^ iperTxverbindung in ethanol for a period of 15 seconds, in a 0.2 wt _o '% ige solution (at room temperature, ie, 22 ⁰ C) of silver nitrate in water for a period of 60 seconds

709807/1041

immersed, then washed with water and ethanol and finally dried. This plate is exposed imagewise and without using PS light for a period of 2 minutes any treatment, mounted in a planographic printing machine. In the planographic printing machine, the plate undergoes the usual wetting subjected to water and spreading of paint, whereby the plate is positively colored.

With the printing plate produced in this way, 500 sheets of paper can be produced can be printed.

Table IX

Example inorganic quantity

Organic connection

61 GeS,
0 24 62 GeS ₄ 15th 63 GeS ^ 15th 64 GeS _x 36 example 65

1- (m-caproamidophenyl) -5-mercaptotetrazole

1- (m-caproamidophenyl) -5-mercaptotetrazole

1-phenyl ~ 5-mercaptotetrazole

2-mercapto-5-lauroamidobenzimidazole

A planographic printing plate is made according to Example 64, but with the inorganic material, GeS _x , in an amount

/ 2 '

of 24 / Ug / cm is vaporized. Then the aluminum plate is immersed in a 0.12 wt% solution (at room temperature, ie 22 ⁰ C) of i-phenyl-5-diercaptotetrazole in ethanol for a period of 15 seconds, dried, in a 0.5 wt. - ^ ige solution (at room temperature, ie 22 ⁰ C) of silver nitrate in water for a period of 90 seconds

709807/104

immersed, then washed with water and then with ethanol and finally dried. After doing the so has positively inked the planographic printing plate obtained, 12,000 sheets of paper can be printed with it.

Example 66

According to example 46 is sand-roughened and anodized on a

as in example 1
oxidized aluminum plate \ an inorganic material _f GeSg c _/

at a vacuum of 4.0 χ 10 "^ Torr in a deposit amount of 36 yug / cm. Then the aluminum plate is in a 0.01 wt.% iw; e solution (at room temperature, ie 22 ⁰ C) of p- Dimethylaminobenzylidenrhodamine, p- (CH) -

-NCgH ₄ CH = CHCONHSCS, immersed in ethanol for 15 seconds and then dried. Furthermore, the aluminum plate is immersed in a 0.1% strength by weight solution (90 seconds at 22 ^° C.) of silver nitrate in water and then dried.

The planographic printing plate thus obtained is exposed to PS light for 2 minutes exposed imagewise and then subjected to water wetting and color distribution. Here, m3.11 is given a positive color Printing plate with which 5OO sheets of paper are printed can.

Example 67

According to Beistdel 46, on a sand-roughened aluminum plate,

•, ^. , ^v P ⁿ Example 1 _ ·, ._ ■ _ ·. which has been subjected to anodic oxidation, vaporized on an inorganic material GeS- ,, in a deposition amount of 24 / irg / cm. The vacuum is in this case angexfendete x 10 "5 -. ⁷ Torr Subsequently, the aluminum plate in a 0.12 wt .-% solution (at room temperature, ie, 22 ⁰ C) of i-phenyl-5-mercaptotetrazole in ethanol for a · Immersed for 15 seconds and then dried. Furthermore, the plate is immersed in a 0.5% strength by weight solution (at room temperature, ie 22 ^° C.) of silver nitrate in

709807/1041

Immersed in water for a period of 90 seconds, with water washed, immersed in ethanol and finally dried.

The planographic printing plate material thus obtained is exposed to the PS light for 2 minutes and then, without any other treatment, mounted in a planographic printing machine. If this plate is subjected to water wetting and fine distribution, it becomes colored them positive. With this plate 12,000 sheets of paper can be printed.

Example 68

According to Example 46, on a sand-roughened aluminum plate,

,. . jT. η · j ⁿ Jiph Example 1,. .

which has been subjected to anodic oxidation, evaporated _{on an inorganic material, GeS 0} r, in an amount of deposition of 36 ug / cm. The vacuum applied here is 5 × 0 "- ⁷ Torr. This aluminum plate is then immersed in a 0.06% strength by weight solution (at room temperature, ie 22 ^° C.) of i-phenyl-5-mercaptotetrazole in ethanol for a period of time immersed for 15 seconds and then dried. then, the plate is in a 0.5 wt .-% solution (at room temperature, ie, C 22 ⁰⁾ immersed silver nitrate in water üiir a period of 60 seconds, washed with water, in ethanol dipped and finally dried. Furthermore, the plate in a 0.06 wt .-% solution at room temperature (ie, 22 ⁰ C) of 3- (p-Caproamidophenyl) -4-ethyl-5-mercapto-1,2 , 4-triazole in ethanol for a period immersed for 15 seconds and then dried ^r.

The planographic printing plate obtained in this way is exposed to the PS light for 2 minutes and then the water wetting and color distribution subjected, whereby the plate is positively colored. About 1000 sheets of paper can be printed with this printing plate.

709807/1041

Example- 69

According to Example 1, an inorganic material, GeS ₀ i-, is deposited on an aluminum plate in an amount of

ρ ^c - ^ y ρ

36 ug / cm, thiourea at 1.0 / Ug / cm, silver in an amount of 6.0 ug / cm and 2-mercapto-5-lauroamidobenzimidazole in an amount of 0.5 ug / cm in the order given vaporized.

The planographic printing plate material obtained in this way is exposed for 2 minutes using the Jet Printer 2000 and then exposed subject to water wetting and color distribution. Here a positively colored planographic printing plate is obtained with which about 5000 sheets of paper can be printed.

Example 71

According to Example 1, an inorganic material, GeS ₀ r, in an amount of deposition of 36 ug / cm, antimony in an amount of 2.4 ug / cm, 1-phenyl-5-mercaptotetrazole in an amount of 1 , 0 µg / cm, and silver in an amount of 6.0 µg / cm in the order given. The printing plate material obtained in this way is exposed to PS light for 2 minutes and then subjected to water wetting and color distribution. This results in a positively colored print plate with which about 2000 sheets of paper can be printed.

Example 72

Example 71 is repeated, but using 1.0 ug / cm copper iodide can be used instead of 2.4 µg / cm antimony. Man obtains the same results as in Example 71

Example 73

According to Example 71, after the vacuum deposition of GeS ₀ t-, i-phenyl-5-mercaptotetrazole in a deposition rate of 0.6

P P

/ Ug / cm, silver in the amount of 6.0 ug / cm, and then copper in

709807/1041

at an amount of 4.8 Hg / cm. Here one obtains a Flac printing plate material according to the invention. When printing using this printing plate material, one is obtained positively colored planographic printing plate with which about 2000 sheets of paper can be printed.

Examples 74 to 79

In each of these examples, according to Example 1, the roughening with sand and the has been subjected to anodic oxidation according to Example 1,

GeSp c in a deposition amount of 15 / Ug / in at a vacuum of 5 x 10 "x ⁷ Torr, then evaporated the organic compound according to Table X in the specified amount, and finally silver in the specified amount in that order. The planographic printing plate material obtained is exposed to PS light for the duration shown in Table X and then mounted in a planographic printing machine without any other treatment, using conventional planographic printing operations thereon, treatment using dampening water and spreading of color, a negatively colored one is obtained When printing using this plate, 500 to 1000 sheets of paper can be printed.

709807/1041

Table X example

H ■ 77 78 79

Organic connection

Meta nilic acid

SO ₃ H

Urea, p-Hydrobenzoic acid methyl ester

HO M N) -COOCH ₃

Thiourea 1,3,3-T-dimethyl-6'-nitrospiro <indoline -2,2'-benzo-a-pyran)

ßhodamine B (C ₂ H ₅ ) N

COOH amount

0.37

Deposited exposure time

Ag amount ~

6.0

6.0
6 _; 0

'(min) 1

1 2

1.2 6.0 2 0.5 • 0.15 2 0.4 6 _; 2 3

According to Example 1, on an aluminum plate that has been sand-roughened and anodized according to Example 1,

As ₀ S _x in a deposition amount of

^ -5

at a vacuum of 5 ι 10 Torr, and then 1-phenyl-5-mercaptotetrazole in an amount of 1.0 isg / cm and silver in an amount of 6 ^ 0 ug / cm in the order given vaporized. A planographic printing plate material according to the invention is obtained here. This planographic printing plate material is exposed to light (Jet Light 2000) for 3 minutes and then, without any other treatment, mounted in a planographic printing machine. When using conventional planographic printing operations, Treatment with wetting water and distribution of paint, a positively colored planographic printing plate is obtained, with which 500 to 1000 sheets of paper can be printed.

In this example and previous examples where evaporation of the organic compound alone is not carried out it has been found that although the plates have been colored negatively by the color distribution, their printed surfaces are poor, and the differences in oleophilic nature between image and non-image areas are small and that even such properties deteriorate considerably with the lapse of time.

709807/1041

Claims (23)

Claims Λ. Planographic printing plate material, characterized by a support and a photosensitive layer located on the support, the photosensitive layer being composed of (A) an inorganic material, (B) at least one metal and / or a metal compound, and (C) an organic compound, wherein the inorganic material and the metal and / or the metal compound are able to react with one another under the action of electromagnetic radiation, the organic compound is able to impair the reaction between the inorganic material and the metal and / or the metal compound, and inorganic material, metal and / or metal compound and organic compounds are in contact with each other, and in the imagewise application of electromagnetic radiation, a difference in the hydrophilic or oleophilic nature is caused between irradiated areas and non-irradiated areas of the photosensitive layer. 2. Planographic printing plate material according to claim 1, characterized in that g e mark It shows that the carrier is a metal plate, a plastic film, the surface of which has been made hydrophilic is, 'or a composite material in which a metal plate or foil is laminated onto a plastic foil or paper is, represents. 7/1041 3. Planographic printing plate material according to at least one of the claims 1 and 2, characterized in that the carrier is a plate made of aluminum or zinc. 4-. Planographic printing plate material according to at least one of Claims 1 to 3, characterized in that the inorganic material is a chalcogen, a chalcogenide mass, or a halide. 5 · Planographic printing plate material according to at least one of Claims Λ to 4, characterized in that the inorganic material is a mixture containing germanium and sulfur. 6. Planographic printing plate material according to at least one of claims 1 to 5> characterized in that the organic compound from the group of aldehydes, ketones,. Alkylene oxide polymers, carboxylic acids, phenols, amines, hydrazines, compounds containing -CO-NH groups, nitrogen-containing five-membered ring compounds, sulfur-containing five-membered input compounds, oxygen-containing five-membered ring compounds, nitrogen-containing six-membered compounds
Input compounds, heterocyclic compounds, quinones, organic sulfur compounds, dyes and pigments. 7. planographic printing plate material according to at least one of claims 1 to 6, characterized in that the metal Ag, Cu, Ge, Zn, Cd, Au, Pb, Al, Ga, In, Sn, V, Se, 709807 / 1Ö41 Cr, Fe, Tl., Bi, Mg, Μα, Co, Ni, Sb, Te and / or Fb. 8. planographic printing plate material according to claim 7, characterized in that the metal is Ag or Cu. 9. planographic printing plate material according to at least one of claims 1 to 8, characterized in that the metal compound from the group of halides of groups IB, IV B and VI B, sulfides of groups IB, II B and V B, and Group IV, V and VI oxides is selected. 10. Planographic printing plate material according to at least one of claims 1 to 9 »characterized in that containing the organic compound (C) from the group consisting of aldehydes, ketones, carboxylic acids, phenols, amines, hydrazines, sulfur organic compounds, dyes, pigments and spiropyrans is selected. 11. planographic printing plate material according to claim 10, characterized g e indicates that the organic compound (C) is a Is a sulfur-containing organic compound. 12. Planographic printing plate material according to at least one of claims 1 to 11, characterized in that the organic compound (C) is a dye or a pigment. 709807/104 13 · Planographic printing plate material according to at least one of the claims 1 to 12, marked by the fact that the organic compound (C) is a spiropyran. 14. Flaeh printing plate material according to at least one of claims 1 to 13, characterized in that (A), (B). and (C) are each deposited as discontinuous particles with an average particle size νοηγίο A up to 0.5 J *. 15- planographic printing plate material according to at least one of the claims 1 to 14, characterized in that two of (A), (B) and (C) are in the form of discontinuous particles are deposited, and the remaining one component of (A), (B) or (C) is in the form of a layer. 16. Planographic printing plate material according to at least one of claims 1 to 14, characterized in that any of (A), (B) and (C) in the form of discontinuous Particle is deposited and the other two of (A), (B) or (C) are deposited in the form of a layer. 17 · planographic printing plate material according to at least one of claims 1 to 16, characterized in that (A) in an amount of 0.1 to 10 µg / cm ² , (b) in an amount of 0.1 to 30 µg / cm 2 and (C) deposited in an amount of 0.1 to 3 µg / cm ^2. 709807/1041 18. Planographic printing plate material according to claim. 15 »by this gekennz ei c h η et that (A) in an amount of 0.1 P 2 to 10 µg / cm, (B) in an amount of 0.1 to 30 µg / cm and (C) is deposited to a thickness of 300 2 to 10 µ. 19. planographic printing plate material according to claim 15 »thereby characterized in that (A) in an amount of 0.1 2 up to 10 ug / cm, (B) at a thickness of 3OO 2. up to 10 h, and (C) deposited in an amount of 0.1 to 3 µg / cm. 20. Planographic printing plate material according to claim 15 »characterized i characterized in that (A) in a thickness of 300 A j to 10 n, (B) in an amount of 0.1 to 30 μg / cm and (C) j deposited in an amount of 0.1 to 3 µg / cm. . j 21. Planographic printing plate material according to claim 16, characterized in that (A) in an amount of 0.1 to 10 µg / cm, and (B) and (C) each in a thickness of 300 up to 10 a are deposited. 22. Planographic printing plate material according to claim 16, characterized in that (B) in an amount of 0.1 to 30 Hg / cm, and (A) and (C) are each deposited in a thickness of 300% to 10 u. 23. Planographic printing plate material according to claim 16, characterized in that (C) in an amount of 0.1 to 3 µg / cm, and (A) and (B) are each deposited to a thickness of 300 to 10 ia. 709807/1041 Blank page