DE60315491T2 - THERMAL SENSITIVE PRELIMINARY TO A LITHOGRAPHIC PRESSURE PLATE - Google Patents

Description

TECHNICAL FIELD OF THE INVENTION

The The present invention relates to a heat-sensitive lithographic Printing plate precursor.

GENERAL PRIOR ART

at Lithographic printing machines use a so-called Druckmaster like a printing plate mounted on a drum of the printing press. The master surface enters lithographic image and a print is obtained by first printing ink applied to the image and then the color of the master a receiving material, usually paper, is transmitted. In conventional, So-called lithographic wet printing both ink as Also water based fountain solution on the lithographic image, the oleophilic (or hydrophobic, i.e., ink-receptive, water-repellent) Areas and hydrophilic (or oleophobic, i.e. hydrophilic, ink-repelling) Areas constructed, appropriate. In so-called driographic The lithographic image consists of ink-receptive and ink-repellent prints (i.e., color repellent) Areas and will be during of driographic printing, just apply printing ink to the master.

print Master are usually after the so-called computer-to-film process (data-driven film production) obtained where different pre-presses like the choice of typeface, scanning, making color separations, framing, trapping, layout and imposition done digitally and each color separation on a gel graphic film is exposed. After development, the film as Mask for the exposure of an image-forming material, as a printing plate precursor designated, used and after the development of the plate becomes obtained a printing plate, which is used as a master.

A typical printing plate precursor for Computer-to-film method contains a hydrophilic carrier and an imaging layer with radiation-sensitive polymers Layers containing radiation sensitive diazo compounds, dichromate sensitized hydrophilic colloids and a variety of synthetic photopolymers contain. In particular, diazosensitized layer dressings are widely used. For imagewise exposure, as a rule using a film mask in a UV contact copying machine the exposed image areas are insoluble and the non-exposed areas remain soluble in an aqueous-alkaline developer. The printing plate is then Developed with the developer in the non-exposed areas to remove contained diazonium salt or diazo resin. The illuminated Areas thus form the image areas (i.e., the printing areas) of the printing master and thus become such printing plate precursors as "negative working" called. There are also positive-working materials in which the exposed Areas forming non-printing areas, e.g. Plates with a novolak naphthoquinone diazide coating, which is only exposed in the Areas in the developer solved becomes.

Except the The above radiation-sensitive materials are also heat-sensitive Printing plate precursors very popular become. Such thermal materials have the advantage of their Daylight stability and are particularly suitable for use in the so-called computer-to-plate process (direct digital plate imaging) where the plate precursor is exposed directly, i. without the use of a film mask. In the Usually the material is with heat applied or exposed to infrared light and the generated thereby Heat dissolves you (physical) chemical process such as ablation, polymerization, Insolubilization by crosslinking of a polymer, a thermal induced solubilization, decomposition or coagulation of the particles of a thermoplastic polymeric latex.

The known heat-sensitive Printing plate precursors usually contain a hydrophilic carrier and a coating that is an oleophilic polymer that is alkali soluble in the heated ones or irradiated areas (positive working material) or in the unheated one or non-irradiated areas (negative working material), and an IR absorbing compound. Such an oleophilic Polymer is usually a phenolic resin.

In WO 99/01795 there is disclosed a method of making a positive working photoresist pattern on a substrate, wherein the coating composition comprises a polymeric substance having functional groups, whereby the functionalized polymeric substance is insoluble in the developer prior to irradiation but is solubilized therein upon irradiation. Suitable functional groups are known to promote hydrogen bonding. Examples include an amino group, an amide group, a chloro group, a fluoro group, a carbonyl group, a sulfinyl group and a sulfonyl group. This group pen are bound to the polymeric substance through an esterification reaction with the phenolic hydroxyl group to form a rosin ester.

In EP-A 0 934 822 there is described a heat-sensitive lithographic printing plate precursor which comprises a support having an oleophilic surface and a coating over it, the coating containing an IR absorber and a polymer having a phenolic monomer unit wherein at least some of the phenolic hydroxyl groups are esterified. The esterification group may be a naphthylsulfonate group having an -N = NQ substituent, where Q may be a hydroxy-substituted phenyl group.

In EP-A 1 072 432 there is described an image-forming material containing a recording layer formed of a composition whose solubility in water or an aqueous-alkaline solution is changed under the action of light or heat. This recording layer contains a vinylphenol polymer or a phenol polymer in which hydroxyl groups and alkoxy groups are bonded directly to the aromatic hydrocarbon ring. The alkoxy group contains at most 20 carbon atoms.

In US 3,929,488 There is described a photosensitive positive-working printing plate containing an azo dye which is a novolak resin carrying a coloring diazophenyl group on the phenol ring and whose color changes in the presence of the light-decomposing product of a diazonium salt. This color change is based on a protonation of the azo dye nitrogen, which is triggered by the action of the acid generated by the diazonium salt upon exposure. This azo dye is used as an indicator dye to check the exposed areas on the plate. Compared to conventional indicator dyes, this azo dye has an increased solubility in the developer solution and thus does not remain on the plate after development. For this reason, there is no danger of residual amounts of dye that may cause staining on the non-image areas or toning during the printing process. An azo dye most preferred for use as an indicator dye in these photosensitive compositions, which upon protonation may have such a strong color change in the visible spectral region, is an azo dye obtained by azo coupling of diphenylamine-4-diazonium fluoroborate with novolac.

Thereby, that the coating of the printing ink and the dampening water, the while attached to the plate during the printing process The shelf life can be conditioned by the resistance of the coating to liquids, below referred to as "chemical resistance". The most frequently used polymers in these coatings are phenolic resins, it is known from the above-mentioned prior art that the circulation resistance by Modification of such resins over a chemical substitution reaction on the hydroxyl group of Phenol group can be improved. However, as a result of this Modification reaction the number of free hydroxyl groups on the Polymer and, consequently, the solubility of the coating reduced in an alkaline developer. The present in the present Invention proposed modification reaction allows the Chemical resistance to increase the coating and without significant attenuation of Developability of the coating.

BRIEF PRESENTATION OF THE PRESENT INVENTION

task The present invention is to provide a heat-sensitive lithographic printing plate precursor with a heat-sensitive coating with improved chemical resistance of the Coating against hydraulic fluids and printing press chemicals. Solved This object is achieved by the precursor defined in claim 1 the characterizing property that the heat-sensitive coating the precursor contains a polymer having a phenolic monomer unit, wherein the phenyl group of the Phenolmonomereinheit by a group accordingly the structure -N = N-Q, in which the -N = N - group covalently attached to a carbon atom the phenyl group is bonded and Q is an aromatic group, is substituted.

DETAILED DESCRIPTION OF THE PRESENT INVENTION

To the Getting a heat-sensitive lithographic printing plate with improved run resistance It is important to know the chemical resistance of the heat-sensitive Coating against the hydraulic fluids, such as dampening water and printing ink, and the printing press chemicals, like cleaning fluids for the plate, the blanket and the pressure rollers to increase. These are conditioned Printing properties by the composition of the coating, wherein the polymer type is one of the most important factors for this characteristic.

Be solved the objects of the present invention by a heat-sensitive lithographic printing plate precursor having a support having a hydrophilic surface and an oleophilic coating, wherein the coating is an IR absorber and a polymer having a phenolic monomer unit, wherein the Phenyl group of Phenolmonomereinheit by a group accordingly the structure -N = N-Q, in which the -N = N - group covalently attached to a carbon atom the phenyl group is bonded and Q is an aromatic group, is substituted, this substitution group being shown below also referred to as "Azoarylgruppe".

Be solved the objects of the present invention are also characterized by the fact that the oleophilic coating containing this polymer has a improved chemical resistance by the modification of the polymer by the above substitution group with the structure -N = N-Q, in which the -N = N group is covalently attached to a Carbon atom of the phenyl group is bound and Q is an aromatic Means group achieved. The chemical resistance can by means of various exams be measured.

One suitable method for quantifying the chemical resistance is considered an exam 4 described in the examples. A preferred precursor of the invention has a weight loss as determined in test 4 above less than 45%, more preferably less than 35%, and all more preferably less than 20%.

In In the present invention, the substituent Q of the polymer is contains a phenol monomer unit substituted as described above, a aromatic group containing at least one heteroatom from the group consisting of a nitrogen atom, an oxygen atom and a Sulfur atom, preferably a nitrogen atom or sulfur atom, may contain. The heteroatom may belong to the aromatic ring and / or be contained in a bound to the ring substituent.

In the present invention, the substituent Q may have the structure A- (T) _n . In this structure A represents a monocyclic, 5-membered or 6-membered aromatic group or a 5-membered or 6-membered aromatic ring fused to another ring system. By "fused" is meant that two ring systems have two adjacent carbon atoms in common In this structure, n represents an integer between 0 and the maximum number of positions present on the aromatic group A and represents each T group -SO ₂ -NH-R ¹ , -NH-SO ₂ -R ⁴ , -CO-NR ¹ -R ² , -NR ¹ -CO-R ⁴ , -NR ¹ -CO-NR ² -R ³ , -NR ¹ -CS-NR ² - R ³ , -NR ¹ -CO-OR ¹ , -O-CO-NR ¹ -R ² , -O-CO-R ⁴ , -CO-OR ² , -CO-R ³ , -SO ³ -R ¹ , -O-SO ₂ -R ⁴ , -SO ₂ -R ¹ , -SO-R ⁴ , -P (= O) (- OR ¹ ) (- OR ² ), -OP (= O) (- OR ¹ ) (-OR ² ), -NR ¹ -R ² , -OR ² , -SR ² , -N = NR ⁴ , -CN, -NO ² , halide or -MR ¹ , wherein M is a divalent linking group having 1 to 8 carbon atoms means
wherein R ¹ , R ² and R ³ each independently represent a hydrogen atom or an optionally substituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, heterocyclic group, aryl group, heteroaryl group, aralkyl group or heteroaralkyl group,
wherein R ⁴ and R ^{5 represent} an optionally substituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, heterocyclic group, aryl group, heteroaryl group, aralkyl group or heteroaralkyl group,
or wherein at least two groups from the series of R ¹ to R ⁵ together represent the atoms needed to form a cyclic structure.

in der:
X CD³, ND⁴ oder N bedeutet,
Y die zur Bildung eines 5-gliedrigen oder 6-gliedrigen aromatischen Ringes benötigten Atome bedeutet, wobei diese Atome aus der Gruppe bestehend aus CD³, ND⁴, N, S und O gewählt werden,
wobei D¹, D² und D³ ein Wasserstoffatom, eine gegebenenfalls substituierte Alkylgruppe, Alkenylgruppe, Alkynylgruppe, Cycloalkylgruppe, heterocyclische Gruppe, Arylgruppe, Heteroarylgruppe, Aralkylgruppe oder Heteroaralkylgruppe, -SO₂-NH-D⁵, -NH-SO₂-D⁷, -CO-NR⁵-D⁶, -ND⁵-CO-D⁷, -O-CO-D⁷, -CO-O-D⁵, -CO-D⁵, -SO₃-D⁵, -SO₂-D⁵, -SO-D⁷, -P(=O)(-O-D⁵)(-O-D⁶), -ND⁵-D⁶, -O-D⁵, -S-D⁵, -CN, -NO₂, ein Halogenatom oder -M-D⁵, wobei M eine zweiwertige Verbindungsgruppe mit 1 bis 8 Kohlenstoffatomen bedeutet, darstellen,
wobei D⁴, D⁵ und D⁶ unabhängig voneinander jeweils ein Wasserstoffatom oder eine gegebenenfalls substituierte Alkylgruppe, Alkenylgruppe, Alkynylgruppe, Cycloalkylgruppe, heterocyclische Gruppe, Arylgruppe, Heteroarylgruppe, Aralkylgruppe oder Heteroaralkylgruppe bedeuten,
wobei D⁷ eine gegebenenfalls substituierte Alkylgruppe, Alkenylgruppe, Alkynylgruppe, Cycloalkylgruppe, heterocyclische Gruppe, Arylgruppe, Heteroarylgruppe, Aralkylgruppe oder Heteroaralkylgruppe bedeutet,
oder wobei zumindest zwei Gruppen aus der Reihe von D¹ bis D⁷ gemeinsam die zur Bildung einer cyclischen Struktur benötigten Atome bedeuten.In the present invention, the substitution group -N = NQ may correspond to the formula:

in the:
X is CD ³ , ND ⁴ or N,
Y represents the atoms required to form a 5-membered or 6-membered aromatic ring, these atoms being selected from the group consisting of CD ³ , ND ⁴ , N, S and O,
wherein D ¹ , D ² and D ^{3 represent} a hydrogen atom, an optionally substituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, heterocyclic group, aryl group, heteroaryl group, aralkyl group or heteroaralkyl group, -SO ₂ -NH-D ⁵ , -NH-SO ₂ -D ⁷ , -CO-NR ⁵ -D ⁶ , -ND ⁵ -CO-D ⁷ , -O-CO-D ⁷ , -CO-OD ⁵ , -CO-D ⁵ , -SO ₃ -D ⁵ , -SO ₂ -D ⁵ , -SO-D ⁷ , -P (= O) (- OD ⁵ ) (- OD ⁶ ), -ND ⁵ -D ⁶ , -OD ⁵ , -SD ⁵ , -CN, -NO ₂ Halogen atom or -MD ⁵ , where M is a divalent linking group having 1 to 8 carbon atoms,
wherein D ⁴ , D ⁵ and D ⁶ are each independently a hydrogen atom or an optionally substituted mean alkyl group, alkenyl group, alkynyl group, cycloalkyl group, heterocyclic group, aryl group, heteroaryl group, aralkyl group or heteroaralkyl group,
wherein D ^{7 represents} an optionally substituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, heterocyclic group, aryl group, heteroaryl group, aralkyl group or heteroaralkyl group,
or wherein at least two groups from the series of D ¹ to D ⁷ together represent the atoms needed to form a cyclic structure.

in der:
Z¹ und Z² unabhängig voneinander jeweils CE¹ oder N bedeuten,
wobei E¹ ein Wasserstoffatom oder eine gegebenenfalls substituierte Alkylgruppe, Alkenylgruppe, Alkynylgruppe, Cycloalkylgruppe, heterocyclische Gruppe, Arylgruppe, Heteroarylgruppe, Aralkylgruppe oder Heteroaralkylgruppe bedeutet,
p 0, 1, 2, 3 oder 4 bedeutet,
r 0, 1, 2 oder 3 bedeutet,
E² und E³ unabhängig voneinander jeweils ein Wasserstoffatom, eine gegebenenfalls substituierte Alkylgruppe, Alkenylgruppe, Alkynylgruppe, Cycloalkylgruppe, heterocyclische Gruppe, Arylgruppe, Heteroarylgruppe, Aralkylgruppe oder Heteroaralkylgruppe, -SO₂-NH-E⁴, -NH-SO₂-E⁶, -CO-NE⁴-E⁵, -NE⁴-CO-E⁶, -O-CO-E⁶, -CO-O-E⁴, -CO-E⁴, -SO₃-E⁴, -SO₂-E⁴, -SO-E⁶, -P(=O)(-O-E⁴)(-O-E⁵), -NE⁴-E⁵, -O-E⁴, -S-E⁴, -CN, -NO₂, ein Halogenatom oder -M-E⁴, wobei M eine zweiwertige Verbindungsgruppe mit 1 bis 8 Kohlenstoffatomen bedeutet, darstellen,
wobei E⁴ und E⁵ unabhängig voneinander jeweils ein Wasserstoffatom oder eine gegebenenfalls substituierte Alkylgruppe, Alkenylgruppe, Alkynylgruppe, Cycloalkylgruppe, heterocyclische Gruppe, Arylgruppe, Heteroarylgruppe, Aralkylgruppe oder Heteroaralkylgruppe bedeuten,
wobei E⁶ eine gegebenenfalls substituierte Alkylgruppe, Alkenylgruppe, Alkynylgruppe, Cycloalkylgruppe, heterocyclische Gruppe, Arylgruppe, Heteroarylgruppe, Aralkylgruppe oder Heteroaralkylgruppe bedeutet,
oder wobei zumindest zwei Gruppen aus der Reihe von E¹ bis E⁶ gemeinsam die zur Bildung einer cyclischen Struktur benötigten Atome bedeuten.In the present invention, the substitution group -N = NQ may correspond to the formula:

in the:
Z ¹ and Z ² are each independently of one another CE ¹ or N,
wherein E ^{1 represents} a hydrogen atom or an optionally substituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, heterocyclic group, aryl group, heteroaryl group, aralkyl group or heteroaralkyl group,
p is 0, 1, 2, 3 or 4,
r is 0, 1, 2 or 3,
E ² and E ³ are each independently hydrogen, optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, heterocyclic, aryl, heteroaryl, aralkyl or heteroaralkyl, -SO ₂ -NH-E ⁴ , -NH-SO ₂ -E ⁶ , -CO-NE ⁴ -E ⁵ , -NE ⁴ -CO-E ⁶ , -O-CO-E ⁶ , -CO-OE ⁴ , -CO-E ⁴ , -SO ₃ -E ⁴ , -SO ₂ - E ⁴ , -SO-E ⁶ , -P (= O) (- OE ⁴ ) (- OE ⁵ ), -NE ⁴ -E ⁵ , -OE ⁴ , -SE ⁴ , -CN, -NO ₂ , a halogen atom or -ME ⁴ , where M is a bivalent linking group having 1 to 8 carbon atoms,
wherein E ⁴ and E ⁵ each independently represent a hydrogen atom or an optionally substituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, heterocyclic group, aryl group, heteroaryl group, aralkyl group or heteroaralkyl group,
wherein E ^{6 represents} an optionally substituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, heterocyclic group, aryl group, heteroaryl group, aralkyl group or heteroaralkyl group,
or wherein at least two groups from the series of E ¹ to E ⁶ together represent the atoms needed to form a cyclic structure.

in der:
q 0, 1, 2, 3, 4 oder 5 bedeutet,
F¹ ein Wasserstoffatom oder eine gegebenenfalls substituierte Alkylgruppe, Alkenylgruppe, Alkynylgruppe, Cycloalkylgruppe, heterocyclische Gruppe, Arylgruppe, Heteroarylgruppe, Aralkylgruppe oder Heteroaralkylgruppe, -SO₂-NH-F², -NH-SO₂-F⁴, -CO-NF²-F³, -NF²-CO-F⁴, -O-CO-F⁴, -CO-O-F², -CO-F², -SO₃-F², -SO₂-F², -SO-F4, -P(=O)(-O-F²)(-O-F³), -NF²-F³, -O-F², -S-F², -CN, -NO₂, ein Halogenatom oder -M-F², wobei M eine zweiwertige Verbindungsgruppe mit 1 bis 8 Kohlenstoffatomen bedeutet, darstellt,
wobei F² und F³ unabhängig voneinander jeweils ein Wasserstoffatom oder eine gegebenenfalls substituierte Alkylgruppe, Alkenylgruppe, Alkynylgruppe, Cycloalkylgruppe, heterocyclische Gruppe, Arylgruppe, Heteroarylgruppe, Aralkylgruppe oder Heteroaralkylgruppe bedeuten,
wobei F⁴ eine gegebenenfalls substituierte Alkylgruppe, Alkenylgruppe, Alkynylgruppe, Cycloalkylgruppe, heterocyclische Gruppe, Arylgruppe, Heteroarylgruppe, Aralkylgruppe oder Heteroaralkylgruppe bedeutet,
oder wobei zumindest zwei Gruppen aus der Reihe von F¹ bis F⁴ gemeinsam die zur Bildung einer cyclischen Struktur benötigten Atome bedeuten.In the present invention, the substitution group -N = NQ may correspond to the formula:

in the:
q is 0, 1, 2, 3, 4 or 5,
F ^{1 represents} a hydrogen atom or an optionally substituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, heterocyclic group, aryl group, heteroaryl group, aralkyl group or heteroaralkyl group, -SO ₂ -NH-F ² , -NH-SO ₂ -F ⁴ , -CO-NF ² -F ³ , -NF ² -CO-F ⁴ , -O-CO-F ⁴ , -CO-OF ² , -CO-F ² , -SO ₃ -F ² , -SO ₂ -F ² , -SO- F4, -P (= O) (- OF ²⁾ (- OF ^3), -NF ² -F ^3, -OF ² -SF ^2, -CN, -NO _2, a halogen atom or -MF ^2, wherein M represents a divalent linking group having 1 to 8 carbon atoms,
wherein F ² and F ³ each independently represent a hydrogen atom or an optionally substituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, heterocyclic group, aryl group, heteroaryl group, aralkyl group or heteroaralkyl group,
wherein F ^{4 represents} an optionally substituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, heterocyclic group, aryl group, heteroaryl group, aralkyl group or heteroaralkyl group,
or wherein at least two groups from the series of F ¹ to F ⁴ together represent the atoms needed to form a cyclic structure.

in der:
p 0, 1, 2, 3 oder 4 bedeutet,
G¹ ein Wasserstoffatom, eine gegebenenfalls substituierte Alkylgruppe, Alkenylgruppe, Alkynylgruppe, Cycloalkylgruppe, heterocyclische Gruppe, Arylgruppe, Heteroarylgruppe, Aralkylgruppe oder Heteroaralkylgruppe, -SO₂-NH-G², -NH-SO₂-G⁴, -CO-NG²-G³, -NG²-CO-G⁴, -O-CO-G⁴, -CO-O-G², -CO-G², -SO₃-G², -SO₂-G², -SO-G⁴, -P(=O)(-O-G²)(-O-G³), -NG²-G³, -O-G², -S-G², -CN, -NO₂, ein Halogenatom oder -M-G², wobei M eine zweiwertige Verbindungsgruppe mit 1 bis 8 Kohlenstoffatomen bedeutet, darstellt, Z³ O, S oder NG⁵ bedeutet,
wobei G², G³ und G⁵ unabhängig voneinander jeweils ein Wasserstoffatom oder eine gegebenenfalls substituierte Alkylgruppe, Alkenylgruppe, Alkynylgruppe, Cycloalkylgruppe, heterocyclische Gruppe, Arylgruppe, Heteroarylgruppe, Aralkylgruppe oder Heteroaralkylgruppe bedeuten,
wobei G⁴ eine gegebenenfalls substituierte Alkylgruppe, Alkenylgruppe, Alkynylgruppe, Cycloalkylgruppe, heterocyclische Gruppe, Arylgruppe, Heteroarylgruppe, Aralkylgruppe oder Heteroaralkylgruppe bedeutet,
oder wobei zumindest zwei Gruppen aus der Reihe von G¹ bis G⁵ gemeinsam die zur Bildung einer cyclischen Struktur benötigten Atome bedeuten.In the present invention, the substitution group -N = NQ may correspond to the formula:

in the:
p is 0, 1, 2, 3 or 4,
G ^{1 represents} a hydrogen atom, an optionally substituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, heterocyclic group, aryl group, heteroaryl group, aralkyl group or heteroaralkyl group, -SO ₂ -NH-G ² , -NH-SO ₂ -G ⁴ , -CO-NG ² -G ³ , -NG ² -CO-G ⁴ , -O-CO-G ⁴ , -CO-OG ² , -CO-G ² , -SO ₃ -G ² , -SO ₂ -G ² , -SO- G ⁴ , -P (= O) (- OG ² ) (- OG ³ ), -NG ² -G ³ , -OG ² , -SG ² , -CN, -NO ₂ , a halogen atom or -MG ² , wherein M represents a divalent linking group having 1 to 8 carbon atoms, Z ^{3 represents} O, S or NG ⁵ ,
wherein G ² , G ³ and G ⁵ each independently represent a hydrogen atom or an optionally substituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, heterocyclic group, aryl group, heteroaryl group, aralkyl group or heteroaralkyl group,
wherein G ^{4 represents} an optionally substituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, heterocyclic group, aryl group, heteroaryl group, aralkyl group or heteroaralkyl group,
or wherein at least two groups from the series of G ¹ to G ⁵ together represent the atoms needed to form a cyclic structure.

in der:
r 0, 1, 2 oder 3 bedeutet,
U¹ ein Wasserstoffatom, eine gegebenenfalls substituierte Alkylgruppe, Alkenylgruppe, Alkynylgruppe, Cycloalkylgruppe, heterocyclische Gruppe, Arylgruppe, Heteroarylgruppe, Aralkylgruppe oder Heteroaralkylgruppe, -SO₂-NH-U², -NH-SO₂-U⁴, -CO-NU²-U³, -NU²-CO-U⁴, -O-CO-U⁴, -CO-O-U², -CO-U², -SO₃-U², -SO₂-U², -SO-U⁴, -P(=O)(-O-U²)(-O-U³), -NU²-U³, -O-U², -S-U², -CN, -NO₂, ein Halogenatom oder -M-U², wobei M eine zweiwertige Verbindungsgruppe mit 1 bis 8 Kohlenstoffatomen bedeutet, darstellt,
wobei U², U³, U⁵ und U⁶ unabhängig voneinander jeweils ein Wasserstoffatom oder eine gegebenenfalls substituierte Alkylgruppe, Alkenylgruppe, Alkynylgruppe, Cycloalkylgruppe, heterocyclische Gruppe, Arylgruppe, Heteroarylgruppe, Aralkylgruppe oder Heteroaralkylgruppe bedeuten,
wobei U⁴ eine gegebenenfalls substituierte Alkylgruppe, Alkenylgruppe, Alkynylgruppe, Cycloalkylgruppe, heterocyclische Gruppe, Arylgruppe, Heteroarylgruppe, Aralkylgruppe oder Heteroaralkylgruppe bedeutet,
oder wobei zumindest zwei Gruppen aus der Reihe von U¹ bis U⁴ gemeinsam die zur Bildung einer cyclischen Struktur benötigten Atome bedeuten oder
wobei U⁵ und U⁶ gemeinsam die zur Bildung einer cyclischen Struktur benötigten Atome bedeuten.In the present invention, the substitution group -N = NQ may correspond to the formula:

in the:
r is 0, 1, 2 or 3,
U ^{1 is} a hydrogen atom, an optionally substituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, heterocyclic group, aryl group, heteroaryl group, aralkyl group or heteroaralkyl group, -SO ₂ -NH-U ² , -NH-SO ₂ -U ⁴ , -CO-NU ² -U ³ , -NU ² -CO-U ⁴ , -O-CO-U ⁴ , -CO-OU ² , -CO-U ² , -SO ₃ -U ² , -SO ₂ -U ² , -SO- U ⁴ , -P (= O) (-OU ² ) (-OU ³ ), -NU ² -U ³ , -OU ² , -SU ² , -CN, -NO ₂ , a halogen atom or -MU ² , wherein M represents a divalent linking group having 1 to 8 carbon atoms,
wherein U ² , U ³ , U ⁵ and U ⁶ each independently represent a hydrogen atom or an optionally substituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, heterocyclic group, aryl group, heteroaryl group, aralkyl group or heteroaralkyl group,
wherein U ^{4 represents} an optionally substituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, heterocyclic group, aryl group, heteroaryl group, aralkyl group or heteroaralkyl group,
or wherein at least two groups from the series of U ¹ to U ⁴ together represent the atoms needed to form a cyclic structure, or
wherein U ⁵ and U ⁶ together represent the atoms needed to form a cyclic structure.

in der:
r 0, 1, 2 oder 3 bedeutet,
p 0, 1, 2, 3 oder 4 bedeutet,
V¹ und V² unabhängig voneinander jeweils ein Wasserstoffatom, eine gegebenenfalls substituierte Alkylgruppe, Alkenylgruppe, Alkynylgruppe, Cycloalkylgruppe, heterocyclische Gruppe, Arylgruppe, Heteroarylgruppe, Aralkylgruppe oder Heteroaralkylgruppe, -SO₂-NH-V³, -NH-SO₂-V⁵, -CO-NV³-V⁴, -NV³-CO-V⁵, -O-CO-V⁵, -CO-O-V³, -CO-V³, -SO₃-V³, -SO₂-V³, -SO-V⁵, -P(=O)(-O-V³)(-O-V⁴), -NV³-V⁴, -O-V³, -S-V³, -CN, -NO₂, ein Halogenatom oder -M-V³, wobei M eine zweiwertige Verbindungsgruppe mit 1 bis 8 Kohlenstoffatomen bedeutet, darstellen,
wobei V³ und V⁴ unabhängig voneinander jeweils ein Wasserstoffatom oder eine gegebenenfalls substituierte Alkylgruppe, Alkenylgruppe, Alkynylgruppe, Cycloalkylgruppe, heterocyclische Gruppe, Arylgruppe, Heteroarylgruppe, Aralkylgruppe oder Heteroaralkylgruppe bedeuten,
wobei V⁵ eine gegebenenfalls substituierte Alkylgruppe, Alkenylgruppe, Alkynylgruppe, Cycloalkylgruppe, heterocyclische Gruppe, Arylgruppe, Heteroarylgruppe, Aralkylgruppe oder Heteroaralkylgruppe bedeutet,
oder wobei zumindest zwei Gruppen aus der Reihe von V¹ bis V⁵ gemeinsam die zur Bildung einer cyclischen Struktur benötigten Atome bedeuten.In the present invention, the substitution group -N = NQ may correspond to the formula:

in the:
r is 0, 1, 2 or 3,
p is 0, 1, 2, 3 or 4,
Each of V ¹ and V ² independently represents a hydrogen atom, an optionally substituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, heterocyclic group, aryl group, heteroaryl group, aralkyl group or heteroaralkyl group, -SO ₂ -NH-V ³ , -NH-SO ₂ -V ⁵ , -CO-NV ³ -V ⁴ , -NV ³ -CO-V ⁵ , -O-CO-V ⁵ , -CO-OV ³ , -CO-V ³ , -SO ₃ -V ³ , -SO ₂ - V ³ , -SO-V ⁵ , -P (= O) (- OV ³ ) (- OV ⁴ ), -NV ³ -V ⁴ , -OV ³ , -SV ³ , -CN, -NO ₂ , a halogen atom or -MV ³ , where M is a bivalent linking group having 1 to 8 carbon atoms,
wherein V ³ and V ⁴ each independently represent a hydrogen atom or an optionally substituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, heterocyclic group, aryl group, heteroaryl group, aralkyl group or heteroaralkyl group,
wherein V ^{5 represents} an optionally substituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, heterocyclic group, aryl group, heteroaryl group, aralkyl group or heteroaralkyl group,
or wherein at least two groups from the series of V ¹ to V ⁵ together represent the atoms needed to form a cyclic structure.

in der:
r 0, 1, 2 oder 3 bedeutet,
W¹ ein Wasserstoffatom, eine gegebenenfalls substituierte Alkylgruppe, Alkenylgruppe, Alkynylgruppe, Cycloalkylgruppe, heterocyclische Gruppe, Arylgruppe, Heteroarylgruppe, Aralkylgruppe oder Heteroaralkylgruppe, -SO₂-NH-W², -NH-SO₂-W⁴, -CO-NW²-W³, -NU²-CO-W⁴, -O-CO-W⁴, -CO-O-W², -CO-W², -SO₃-W², -SO₂-W², -SO-W⁴, -P(=O)(-O-W²)(-O-W³), -NW²-W³, -O-W², -S-W², -CN, -NO₂, ein Halogenatom oder -M-W², wobei M eine zweiwertige Verbindungsgruppe mit 1 bis 8 Kohlenstoffatomen bedeutet, darstellt,
wobei W², W³, W⁵ und W⁶ unabhängig voneinander jeweils ein Wasserstoffatom oder eine gegebenenfalls substituierte Alkylgruppe, Alkenylgruppe, Alkynylgruppe, Cycloalkylgruppe, heterocyclische Gruppe, Arylgruppe, Heteroarylgruppe, Aralkylgruppe oder Heteroaralkylgruppe bedeuten,
wobei W⁴ eine gegebenenfalls substituierte Alkylgruppe, Alkenylgruppe, Alkynylgruppe, Cycloalkylgruppe, heterocyclische Gruppe, Arylgruppe, Heteroarylgruppe, Aralkylgruppe oder Heteroaralkylgruppe bedeutet,
oder wobei zumindest zwei Gruppen aus der Reihe von W¹ bis W⁶ gemeinsam die zur Bildung einer cyclischen Struktur benötigten Atome bedeuten.In the present invention, the substitution group -N = NQ may correspond to the formula:

in the:
r is 0, 1, 2 or 3,
W ^{1 represents} a hydrogen atom, an optionally substituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, heterocyclic group, aryl group, heteroaryl group, aralkyl group or heteroaralkyl group, -SO ₂ -NH-W ² , -NH-SO ₂ -W ⁴ , -CO-NW ² -W ³ , -NU ² -CO-W ⁴ , -O-CO-W ⁴ , -CO-OW ² , -CO-W ² , -SO ₃ -W ² , -SO ₂ -W ² , -SO- W ⁴ , -P (= O) (- OW ² ) (- OW ³ ), -NW ² -W ³ , -OW ² , -SW ² , -CN, -NO ₂ , a halogen atom or -MW ² , wherein M represents a divalent linking group having 1 to 8 carbon atoms,
wherein W ² , W ³ , W ⁵ and W ⁶ each independently represent a hydrogen atom or an optionally substituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, heterocyclic group, aryl group, heteroaryl group, aralkyl group or heteroaralkyl group,
wherein W ^{4 represents} an optionally substituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, heterocyclic group, aryl group, heteroaryl group, aralkyl group or heteroaralkyl group,
or wherein at least two groups from the series of W ¹ to W ⁶ together represent the atoms needed to form a cyclic structure.

The used according to the invention Polymers can prepared by various methods, e.g. by reaction a polymer having a phenolic monomer unit with a diazonium salt or by reaction of a phenolic monomer with a diazonium salt and subsequent Polymerizing or polycondensing this reacted monomer. These pre-modified monomers may preferably be used with others Monomers copolymerized or copolycondensed.

in der Q eine aromatische Gruppe und R ein Wasserstoffatom oder einen Substituenten wie eine Alkylgruppe ist.The reaction of a diazonium salt with a phenol group under alkaline conditions gives a coupling of a diazo group to the aromatic ring structure and is illustrated schematically in the following general reaction scheme:

wherein Q is an aromatic group and R is a hydrogen atom or a substituent such as an alkyl group.

The diazonium salts used for the purpose of the present application can be prepared by diazotization of a corresponding aromatic amine to which a diazotizing agent such as a nitrite salt is added to the amine in the presence of an acid such as HCl, H ₂ SO ₄ or H ₃ PO ₄ . Most diazonium salts are relatively stable at low temperature, such as at a temperature between about 0 ° C and about 5 ° C, and soluble in water or a mixture of water and an organic solvent such as acetic acid or 1-methoxy-2-propanol. A solution of the diazonium salt may be used for further reaction with a solution of a polymer having phenolic groups. By this azo coupling reaction, an aromatic diazo group is substituted on the aromatic ring structure of the phenol group. This azo coupling may occur ortho or para on the hydroxyl group, depending on the position of such coupling, for example, depending on the position in which the polycondensation reaction of the phenolic monomer compounds with formaldehyde has taken place.

AM-02:

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Examples of aromatic amines diazotizable to a diazonium salt, where the diazonium salt can then be used in an azo coupling with a phenolic group, are the following compounds: AM-01:

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AT THE 14TH:

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AT 19:

ON 20:

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ON THE 27TH:

ON THE 28TH:

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AM 36:

polymers with phenolic monomer units a random copolymer, an alternating copolymer, a block copolymer or a graft copolymer of different monomers. When suitable examples are polymers or copolymers of vinylphenol, To name novolac resins or Resolharze. Preference is given to a novolak resin.

The Novolak resin or Resolharz can by polycondensation of at least an element selected from the group consisting of aromatic hydrocarbons, such as phenol, o-cresol, p-cresol, m-cresol, 2,5-xylenol, 3,5-xylenol, resorcinol, pyrogallol, Bisphenol, bisphenol A, trisphenol, o-ethylphenol, p-ethylphenol, propylphenol, n-butylphenol, t-butylphenol, 1-naphthol and 2-naphthol, with at least one aldehyde or ketone from the group consisting of aldehydes, such as formaldehyde, glyoxal, Acetoaldehyde, propionaldehyde, benzaldehyde and furfural, and ketones, such as acetone, methyl ethyl ketone and methyl isobutyl ketone, in the presence of a acid catalyst getting produced. Instead of formaldehyde and acetaldehyde can also Paraformaldehyde or paraldehyde be used.

The by gel permeation chromatography based on a universal Calibration with polystyrene standards measured weight average molecular weight of the novolak resin is preferably between 500 and 150,000 g / mol, more preferably between 1,500 and 15,000 g / mol.

The poly (vinylphenol) resin may also be a polymer consisting of one or more hydroxyphenyl-containing monomers, such as hydroxystyrenes or hydroxyphenyl (meth) acrylates. Examples of such hydroxystyrenes are o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, 2- (o-hydroxyphenyl) -propylene, 2- (m-hydroxyphenyl) -propylene and 2- (p-hydroxyphenyl) -propylene. Such a hydroxystyrene may be substituted on its aromatic ring by a substituent such as chlorine, bromine, iodine, fluorine or a C _1-4 alkyl group. An example of such a hydroxyphenyl (meth) acrylate is 2-hydroxyphenyl methacrylate.

The Poly (vinylphenol) resin can usually by polymerizing one or more hydroxyphenyl-containing monomers in the presence of a radical polymerization initiator or initiator for cationic Polymerization can be produced. The poly (vinylphenol) resin can also by copolymerizing one or more of these hydroxyphenylhaltigen Monomers with other monomeric compounds, such as acrylate monomers, Methacrylate monomers, acrylamide monomers, methacrylamide monomers, Vinyl monomers, aromatic vinyl monomers or diene monomers, getting produced.

The by gel permeation chromatography based on a universal Calibration with polystyrene standards measured weight average molecular weight of the poly (vinylphenol) resin is preferably between 1,000 and 200,000 g / mol, more preferably between 1,500 and 50,000 g / mol.

Examples of polymers containing diazonium salt-modifiable phenolic monomer units include:
POL-01: ALNOVOL SPN452 is a 40% by weight solution of a novolak resin in Dowanol PM (available by CLARIANT GmbH). Dowanol PM consists of 1-methoxy-2-propanol (> 99.5%) and 2-methoxy-1-propanol (<0.5%).
POL-02: ALNOVOL SPN400 is a 44% by weight solution of a novolak resin in Dowanol PMA (available from CLARIANT GmbH). Dowanol PMA consists of 2-methoxy-1-methylethyl acetate.
POL-03: ALNOVOL HPN100 is a novolak resin available from CLARIANT GmbH.
POL-04: DURITE PD443 is a by board CHEM. INC. available novolak resin.
POL-05: DURITE SD423A is a BY-BOARD CHEM. INC. available novolak resin.
POL-06: DURITE SD126A is a BY-BOARD CHEM. INC. available novolak resin.
POL-07: BAKELITS 6866LB02 is a novolak resin available from BAKELITS AG.
POL-08: BAKELITS 6866LB03 is a novolak resin available from BAKELITS AG.
POL-09: KR 400/8 is manufactured by KOYO CHEMICALS INC. available novolak resin.
POL-10: HRJ 1085 is one by SCHNECTADY INTERNATIONAL INC. available novolak resin.
POL-11: HRJ 2606 is one of SCHNECTADY INTERNATIONAL INC. available phenol novolak resin.
POL-12: LYNCUR CMM is a copolymer of 4-hydroxystyrene and methyl methacrylate available from SIBER HEGNER.

The inventive polymer may contain more than one type of azoaryl group. In such case, the different types of azoaryl groups are inserted one after the other, however, one can also use a mixture of different diazonium salts react on the polymer. Preferably, each type of Azoarylgruppe in an amount between 0.5 mol% and 80 mol%, especially preferably between 1 mol% and 60 mol%, most preferably between 2 mol% and 50 mol%, incorporated into the polymer.

other Polymers, such as unmodified phenolic resins, may also be added to the coating composition be added. The polymer of the invention is preferably in a relationship between 5% by weight and 98% by weight, more preferably between 10 Wt .-% and 95 wt .-%, based on the total weight of the coating, added to the coating composition.

Consists the heat sensitive Coating of more than one layer is the polymer of the invention in at least one of these layers, e.g. in a topcoat. The polymer may also be present in more than one layer of the coating, e.g. in a cover layer and an intermediate layer.

Of the carrier has a hydrophilic surface on or is provided with a hydrophilic layer. The carrier can a sheet-like material such as a plate or a cylindrical one Element like a sleeve-shaped plate be pushed around a printing drum of a printing press can. Preferably, the carrier a metal carrier like a carrier made of aluminum or stainless steel.

One Particularly preferred lithographic support is an electrochemical roughened and anodized aluminum support.

The Roughening and anodizing of lithographic aluminum supports well known. The roughened used in the material according to the invention aluminum support is preferably an electrochemically roughened carrier. When Acid for the roughening becomes, for example, nitric acid used. The for the roughening used acid contains preferably hydrogen chloride. Also mixtures of e.g. Hydrogen chloride and acetic acid come into question.

The roughened and anodized aluminum support may be subjected to post-processing to improve the hydrophilic properties of the support surface. For example, the aluminum support can be silicated by processing the support surface with a sodium silicate solution at elevated temperature, eg 95 ° C. Alternatively, a phosphate processing may be performed wherein the alumina surface is processed with an optional further inorganic fluoride-containing phosphate solution. Further, the alumina surface may be rinsed with an organic acid and / or a salt of an organic acid, eg carboxylic acids, hydroxycarboxylic acids, sulfonic acids or phosphonic acids, or their salts, eg succinates, phosphates, phosphonates, sulfates and sulfonates. Preferred is a citric acid or citrate solution. This treatment can be carried out at room temperature or at a slightly elevated temperature between about 30 ° C and 50 ° C. Further post-processing consists of rinsing the alumina surface with a bicarbonate solution. Further, the alumina surface may be treated with polyvinylphosphonic acid, polyvinylmethylphosphonic acid, phosphoric acid esters of polyvinyl alcohol, polyvinylsulfonic acid, polyvinylbenzenesulfonic acid, sulfuric acid esters of polyvinyl alcohol and acetals of Polyvinyl alcohols, which are formed by reaction with a sulfonated aliphatic aldehyde processed. Further, it is obvious that one or more of these post treatments may be performed separately or in combination. More detailed descriptions of these treatments can be found in GB-A 1 084 070 . DE-A 4 423 140 . DE-A 4 417 907 . EP-A 659 909 . EP-A 537 633 . DE-A 4 001 466 . EP-A 292 801 . EP-A 291 760 and U.S. Patent 4,458,005 ,

To a further embodiment can the carrier also a flexible carrier which is coated with a hydrophilic layer, hereinafter referred to as "primer layer" is. The flexible carrier is e.g. Paper, a plastic film, a thin aluminum carrier or a laminate of these materials. Preferred examples of plastic films are a film of polyethylene terephthalate, polyethylene naphthalate, Cellulose acetate, polystyrene, polycarbonate, etc. The plastic film carrier can opaque or translucent be.

The Primer layer is preferably a crosslinked hydrophilic layer, made of a hydrophilic, with a hardener such as formaldehyde, glyoxal, Polyisocyanate or a hydrolyzed tetraalkyl orthosilicate crosslinked Binder is obtained. The latter crosslinking agent becomes special prefers. The strenght the hydrophilic primer layer can vary between 0.2 and 25 μm and is preferably between 1 and 10 microns.

The hydrophilic binder for use in the primer layer e.g. a hydrophilic (co) polymer such as homopolymers and copolymers of vinyl alcohol, acrylamide, methylolacrylamide, methylolmethacrylamide, Acrylic acid, methacrylic acid, Hydroxyethyl acrylate, hydroxyethyl methacrylate or maleic anhydride vinylmethyl ether copolymers. The hydrophilicity of the used (co) polymer or (co) polymer mixture is preferably higher or equal to the hydrophilicity of at least 60% by weight, preferably to 80% by weight hydrolyzed polyvinyl acetate.

The Lot of hardener, in particular tetraalkylorthosilicate, is preferably at least 0.2 parts by weight per part by weight of hydrophilic binder more preferably between 0.5 and 5 parts by weight, especially preferably between 1 part by weight and 3 parts by weight per part by weight hydrophilic binder.

The hydrophilic primer layer can also be substances containing the mechanical Strength and porosity improve the layer. For this purpose can be colloidal silica to be used. The colloidal silica can be in the form of any commercial Water dispersion of colloidal silica with for example one average particle size up to 40 nm, e.g. 20 nm, to be used. In addition, inert particles with a larger grain size than that colloidal silica be added, e.g. silica, as described in J. Colloid and Interface Sci., Vol. 26, 1968, p 62 to 69, by Stöber described, or toner particles or particles with a mean diameter of at least 100 nm, which is are particles of titanium dioxide or other heavy metal oxides. By embedding these particles, the surface of the hydrophilic primer layer with a uniform rough texture microscopic peaks and valleys, as storage for Serving water in background areas.

Specific examples of suitable hydrophilic primer layers for use in the present invention are disclosed in U.S. Patent Nos. 4,135,359 EP-A 601 240 . GB-P 1 419 512 . FR-P 2 300 354 . U.S. Pat. No. 3,971,660 and U.S. Patent 4,284,705 ,

Particularly preferred is a film carrier which is provided with an adhesion-promoting layer, also referred to as carrier layer. Particularly suitable adhesion promoting layers for use in the present invention include a hydrophilic binder and colloidal silica, as described in US 5,256,237 EP-A 619 524 . EP-A 620 502 and EP-A 619 525 , The amount of silica in the adhesion-promoting layer is preferably between 200 mg / m ² and 750 mg / m ² . Further, the ratio of silica to hydrophilic binder is preferably more than 1 and the specific surface area of the colloidal silica is preferably at least 300 m ² / g, more preferably at least 500 m ² / g.

The carrier coating is heat sensitive and preferably for several hours under normal work lighting conditions (Daylight, fluorescent light) are handled. The coating contains preferably not UV-sensitive Compounds that have an absorption maximum in the wavelength range between 200 nm and 400 nm, such as diazo compounds, photoacids, photoinitiators, quinone diazides or sensitizers. Preferably, the coating also contains no Compounds with an absorption maximum in the wavelength range of visible blue and green light between 400 and 600 nm.

To an embodiment the printing plate precursor is positive working, i. after exposure and development are the exposed areas of the oleophilic layer from the carrier remove and form hydrophilic (non-printing) non-image areas, while the unexposed layer areas remain on the support and an oleophilic form (printing) image area. According to another embodiment If the printing plate precursor is negative working, i. the illuminated ones Areas form the image areas.

The Coating may consist of one or more different layers be composed. Except the coating discussed below, the coating may further e.g. an adhesive layer which improves the adhesion of the coating to the support, a covering layer protecting the coating against contamination or mechanical damage and / or a light in heat transforming layer containing an infrared absorbing compound contains contain.

A suitable negative-working pressure plate developable in alkaline medium contains a phenolic resin and a latent Bronsted acid which forms an acid upon heating or IR irradiation. These acids catalyze the crosslinking of the coating in a heating step subsequent to the exposure or heating step, and thus the curing of the exposed areas. Accordingly, the unexposed areas may be washed away by a developer and the underlying hydrophilic substrate exposed. For a more detailed description of such a negative-working printing plate precursor be on US Pat. No. 6,255,042 and US Pat. No. 6,063,544 and referenced the references mentioned in these documents. In such a negative-working printing plate precursor, the polymer used in the present invention is added to the coating composition and at least partially replaces the phenolic resin.

at a positive working lithographic printing plate precursor the coating can be made soluble by applying heat (thermal Solubilization), i. the coating is in non-heated or non-illuminated state resistant against the developer and color attracting, however, when heated or Irradiation with infrared light made so soluble in the developer, that the hydrophilic surface of the carrier to be released.

In addition to the polymer used in the invention, the coating may contain additional polymeric binders which are soluble in an aqueous-alkaline developer. Preferred polymers are phenolic resins, eg novolac, resoles, polyvinyl phenols and carboxyl-substituted polymers. Typical examples of such polymers are described in DE-A 4 007 428 . DE-A 4 027 301 and DE-A 4 445 820 ,

at a preferred positive working lithographic printing plate precursor contains the coating further comprises one or more dissolution inhibitors (dissolution inhibitors). dissolution inhibitor are compounds that are the dissolution rate of the hydrophobic polymer in aqueous-alkaline Reduce developer in the non-exposed areas of the coating. This reduction in dissolution rate is through the during the warming or Exposure generated heat nullified, causing the coating in the exposed Areas quickly in the developer releases. The dissolution inhibitor has a significant margin of dissolution speed the exposed areas and the unexposed areas. Preferably, the dissolution inhibitor such a good margin in solution speed, that the warmed up or exposed coating areas are already completely dissolved in the developer, before the unexposed areas are so attacked by the developer be that the color attractiveness of the coating is impaired. The solution inhibitor (s) can (can) the layer containing the hydrophobic polymer discussed above be added.

The reduction in the rate of dissolution of the unexposed areas of the coating in the developer is preferably due to the interaction between the hydrophobic polymer and the inhibitor which underlies, for example, the formation of a hydrogen bond between the two compounds. Suitable dissolution inhibitors are preferably organic compounds containing at least one aromatic group and one hydrogen bonding site, eg, a carbonyl group, a sulfonyl group, or a nitrogen atom which may be quaternized and part of a heterocyclic ring or an amine substituent of the organic compound. Suitable dissolution inhibitors of this type are described in, for example EP-A 825 927 and EP-A 823 327 ,

Water repellent polymers are another type of suitable dissolution inhibitor. Such polymers appear to improve the resistance of the coating to the developer by repelling the aqueous developer from the coating. The water-repellent polymers may be added to the layer containing the hydrophobic polymer and / or to a separate layer applied to the layer containing the hydrophobic polymer. In the latter embodiment, the water repellent forms the polymer is a barrier layer protecting the coating from the developer, and the solubility of the barrier layer in the developer or the penetrability of the developer in the barrier layer can be increased by exposure to heat or infrared light exposure as described in, eg, US Pat EP-A 864 420 . EP-A 950 517 and WO 99/21725 , Preferred examples of the water-repellent polymers are polymers having siloxane and / or perfluoroalkyl moieties. In one embodiment, the coating contains such a water-repellent polymer in an amount between 0.5 and 25 mg / m ² , preferably between 0.5 and 15 mg / m ² and most preferably between 0.5 and 10 mg / m ² . If the water-repellent polymer used is also color-repelling, for example in the case of polysiloxanes, then there is a risk that amounts above 25 mg / m ² cause a weak color attraction of the unheated or unexposed areas. On the other hand, an amount less than 0.5 mg / m ² may result in unsatisfactory developer resistance. The polysiloxane may be a linear, cyclic or complex crosslinked polymer or copolymer. The term "polysiloxane compound" includes any compound containing more than one siloxane group -Si (R, R ') - O- in which R and R' represent an optionally substituted alkyl or aryl group Preferred siloxanes are phenylalkylsiloxanes and dialkylsiloxanes. The number of siloxane groups in the (co) polymer is at least 2, preferably at least 10, more preferably at least 20. It can be below 100, preferably below 60. In another embodiment, the water-repellent polymer is a block copolymer or graft copolymer of a poly (alkylene oxide) - A suitable copolymer contains about 15 to 25 siloxane units and 50 to 70 alkylene oxide units Preferred examples include copolymers with phenylmethylsiloxane and / or dimethylsiloxane and ethylene oxide and / or propylene oxide such as Tego Glide 410, Tego Wet 265, Tego Protect 5001 or Silikophen P50 / X, all by Tego Chemie, Essen, Germany. As a result of its bifunctional structure, such a copolymer acts as a surfactant during coating, thereby automatically positioning itself at the interface between the coating and the air, forming a separate topcoat, even when the overall coating is made from a single casting solution. At the same time, such surfactants act as spreading agents, which improves the coating quality. The water-repellent polymer may also be applied from a second solution to the layer containing the hydrophobic polymer. In this embodiment, it may be advantageous to use in the second casting solution a solvent which is incapable of dissolving the ingredients contained in the first layer, whereby a highly concentrated water-repellent phase is obtained on the coating.

The coating also preferably contains one or more development accelerators, ie compounds which promote the solution because they are capable of increasing the dissolution rate of the unheated or unexposed coating areas in the developer. The simultaneous use of dissolution inhibitors and solution accelerators allows a precise fine adjustment of the solution behavior of the coating. Suitable dissolution accelerators are cyclic acid anhydrides, phenols or organic acids. Examples of the cyclic acid anhydride include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrachlorophthalic anhydride, maleic anhydride, chloromaleic anhydride, .alpha.-phenylmaleic anhydride, succinic anhydride and pyromellitic anhydride as described in US Pat US Pat. No. 4,115,128 , Examples of the phenols include bisphenol A, p-nitrophenol, p-ethoxyphenol, 2,4,4'-trihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 4-hydroxybenzophenone, 4,4 ', 4 "-trihydroxytriphenylmethane and 4,4 ', 3 ", 4"-tetrahydroxy-3,5,3',5'-tetramethyltriphenylmethane and the like. Examples of the organic acids include sulfonic acids, sulfinic acids, alkylsulfuric acids, phosphonic acids, phosphates and carboxylic acids, as described, for example, in US Pat JP-A 60-88,942 and JP-A 2-96755 , Typical examples of these organic acids include p-toluenesulfonic acid, dodecylbenzenesulfonic acid, p-toluenesulfinic acid, ethylsulfuric acid, phenylphosphonic acid, phenylphosphinic acid, phenylphosphate, diphenylphosphate, benzoic acid, isophthalic acid, adipic acid, p-toluic acid, 3,4-dimethoxybenzoic acid, phthalic acid, terephthalic acid, Cyclohexene-1,2-dicarboxylic acid, erucic acid, lauric acid, n-undecanoic acid and ascorbic acid. The amount of cyclic acid anhydride, phenol or organic acid in the coating is preferably between 0.05 and 20% by weight, based on the coating as a whole.

The a modified according to the invention Phenol monomer unit containing polymer can in conventional radiation-sensitive printing plate precursors are used, wherein at least a portion of the conventional phenolic polymer at least one of the inventively modified polymers is replaced.

IR-1 According to a particularly preferred embodiment, the material according to the invention is image-wise exposed to infrared light which is converted into heat by an infrared-absorbing agent, which may be a dye or pigment having an absorption maximum in the infrared wavelength range. The ratio of the sensitizing dye or pigment in the coating is usually between 0.25 and 10.0 wt .-%, particularly preferably between 0.5 and 7.5 wt .-%, based on the coating as a whole. Preferred infrared absorbing compounds are dyes such as cyanine dyes or merocyanine dyes or pigments such as carbon black. A suitable compound is the following infrared dye:

IR-1

CD-1 The coating may further contain an organic dye that absorbs visible light to give a visible image upon imagewise exposure and subsequent development. Such a dye is often referred to as a contrast dye or indicator dye. A blue dye having an absorption maximum in the wavelength range between 600 nm and 750 nm is preferred. Although the dye absorbs visible light, it preferably does not sensitize the printing plate precursor, ie does not render the coating more soluble in the developer during exposure to visible light. Suitable examples of such a contrast dye are the quaternized triarylmethane dyes. Another suitable compound is the following dye:

CD-1

The Infrared absorbing compound and contrast dye can in the layer containing the hydrophobic polymer and / or in the above-discussed barrier layer and / or in a possible further Layer be included. According to a very particularly preferred embodiment the infrared absorbing compound is in or near the barrier layer concentrated, e.g. in an intermediate layer between the hydrophobic Polymer-containing layer and the barrier layer.

The printing plate precursor according to the invention can be exposed to infrared light by means of an LED or a laser. Preferred for the exposure is a near infrared light having a wavelength between about 750 and about 1500 nm emitting laser, eg, a semiconductor laser diode, a Nd: YAG laser, or a Nd: YLF laser. The laser power required depends on the sensitivity of the imaging layer, the pixel dwell time of the laser beam as determined by the beam width (a typical value at 1 / e ^{2 of} the maximum intensity is between 10 and 25 μm for modern platesetters), the scanning speed and the resolution of the Gelichters (ie the number of addressable pixels per unit length, often expressed in dots per inch or dpi / typical values are between 1,000 and 4,000 dpi).

There are two types of common laser imagers, ie, an internal drum plate imager (ITD disc tray ter) and an external drum platesetter (XTD platesetter). ITD platesetters for thermal plates are usually characterized by very high scanning speeds up to 1,500 m / s and sometimes require a laser power of several watts. The Agfa Galileo T is a typical example of an ITD technology platesetter. XTD platesetters operate at a lower scanning speed, typically between 0.1 m / s and 10 m / s, and have a typical laser power per laser beam between 20 mW and 500 mW. The family of Creo Trendsetter platesetters and the family of Agfa Excalibur platesetters both work on the basis of XTD technology.

The known platesetters are suitable for use as off-press gelators. This option has the advantage of reducing press downtime. XTD platesetter configurations are also suitable for on-press exposure, which has the advantage of immediate registration in a multi-color press. More detailed technical information on on-press-gelichter are eg in US 5,174,205 and US 5,163,368 described.

in the The development step becomes the non-image areas of the coating by immersion in an aqueous-alkaline Developer removed, optionally in combination with mechanical Wipe, e.g. by means of a brush roller. The pH of the developer is preferably above 10, more preferably above 12. At the development step, a rinsing step may a gumming step, a drying step and / or a post-baking step connect.

The printing plate thus obtained is suitable for conventional, so-called wet offset printing, in which printing ink and fountain solution are applied to the plate. In another suitable printing method so-called single-fluid printing ink is used without fountain solution. Single fluid ink is composed of an ink phase, also called the hydrophobic or oleophilic phase, and a polar phase which replaces the fountain solution used in conventional wet offset printing. Suitable examples of single-fluid printing inks are described in US 4,045,232 . US 4,981,517 and US 6,140,392 , In a most preferred embodiment, the single-fluid ink contains a paint phase and a polyol phase as described in US-A-5,466,347 WO 00/32705 ,

EXAMPLES

Preparation of Polymer MP-01:

- Diazonium solution:

A mixture of 3.13 g AM-01, 45 ml 1-methoxy-2-propanol and 9 ml water is stirred and cooled to 5 ° C. Then 4.7 ml of concentrated HCl are added and the mixture is cooled to 0 ° C. Thereafter, a solution of 0.85 g of NaNO ₂ in 5 ml of water is added dropwise and then stirred at 0 ° C for 10 minutes.

Phenol polymer solution:

A mixture of 137.7 g POL-01 solution (40% by weight), 11.5 g NaOAc.3H ₂ O and 225 ml 1-methoxy-2-propanol is stirred and cooled to 0 ° C.

The as above diazonium solution will over The phenol polymer solution was added dropwise for 10 minutes, after which 30 Minutes at 0 ° C and stirring is continued for 2 hours at room temperature. The thus obtained Mixture is then over 30 minutes under constant stir added to 1.5 liters of ice water. The polymer precipitates from the aqueous Medium off and is filtered off. Finally, the desired product is through Wash with water and then Dry at 45 ° C receive.

Preparation of Polymer MP-02:

- Diazonium solution:

A mixture of 6.3 g of AM-01, 90 ml of 1-methoxy-2-propanol and 18 ml of water is stirred and cooled to 5 ° C. Then 9.5 ml of concentrated HCl are added and the mixture is cooled to 0 ° C. Thereafter, a solution of 1.7 g of NaNO ₂ in 18 ml of water is added dropwise and then stirred at 0 ° C for 10 minutes.

Phenol polymer solution:

A mixture of 137.7 g POL-01 solution (40% by weight), 23 g NaOAc.3H ₂ O and 450 ml 1-methoxy-2-propanol is stirred and cooled to 0 ° C.

The as above diazonium solution will over The phenol polymer solution was added dropwise for 20 minutes, after which 30 Minutes at 0 ° C and stirring is continued for 2 hours at room temperature. The thus obtained Mixture is then over With constant stirring for 30 minutes Added 1.5 liters of ice water. The polymer precipitates from the aqueous Medium off and is filtered off. Finally, the desired product is through Wash with water and then Dry at 45 ° C receive.

Preparation of Polymer MP-03:

- Diazonium solution:

A mixture of 12.5 g AM-01, 180 ml 1-methoxy-2-propanol and 36 ml water is stirred and cooled to 5 ° C. Subsequently, 19 ml of concentrated HCl are added and the mixture is cooled to 0 ° C. Thereafter, a solution of 3.4 g of NaNO ₂ in 20 ml of water is added dropwise and then stirred at 0 ° C for 10 minutes.

Phenol polymer solution:

A mixture of 137.7 g of POL-01 solution (40% by weight), 46 g of NaOAc.3H ₂ O and 450 ml of 1-methoxy-2-propanol is stirred and cooled to 0 ° C.

The as above diazonium solution will over The phenol polymer solution was added dropwise for 30 minutes, after which 30 Minutes at 0 ° C and stirring is continued for 2 hours at room temperature. The thus obtained Mixture is then over 30 minutes under constant stir added to 1.5 liters of ice water. The polymer precipitates from the aqueous Medium off and is filtered off. Finally, the desired product is through Wash with water and then Dry at 45 ° C receive.

Preparation of Polymer MP-04:

- Diazonium solution:

A mixture of 31.3 g AM-01, 300 ml 1-methoxy-2-propanol and 90 ml water is stirred and cooled to 5 ° C. Then 47 ml of concentrated HCl are added and the mixture is cooled to 0 ° C. Thereafter, a solution of 8.54 g of NaNO ₂ in 50 ml of water is added dropwise and then stirred at 0 ° C for 10 minutes.

Phenol polymer solution:

A mixture of 137.7 g of POL-01 solution (40% by weight), 115 g of NaOAc.3H ₂ O and 200 ml of 1-methoxy-2-propanol is stirred and cooled to 0 ° C.

The as above diazonium solution will over The phenol polymer solution was added dropwise for 60 minutes, after which 30 Minutes at 0 ° C and stirring is continued for 2 hours at room temperature. The thus obtained Mixture is then over 30 minutes under constant stir added to 1.5 liters of ice water. The polymer precipitates from the aqueous Medium off and is filtered off. Finally, the desired product is through Wash with water and then Dry at 45 ° C receive.

Preparation of Polymer MP-05:

- Diazonium solution:

A mixture of 50 g AM-01, 480 ml 1-methoxy-2-propanol and 145 ml water is stirred and cooled to 5 ° C. Subsequently, 75 ml of concentrated HCl are added and the mixture is cooled to 0 ° C. Thereafter, a solution of 13.6 g of NaNO ₂ in 80 ml of water is added dropwise and then stirred at 0 ° C for 10 minutes.

Phenol polymer solution:

A mixture of 137.7 g POL-01 solution (40% by weight), 184 g NaOAc.3H ₂ O and 400 ml 1-methoxy-2-propanol is stirred and cooled to 0 ° C.

The as above diazonium solution will over The phenol polymer solution was added dropwise for 60 minutes, after which 30 Minutes at 0 ° C and stirring is continued for 2 hours at room temperature. The thus obtained Mixture is then over 30 minutes under constant stir added to 1.5 liters of ice water. The polymer precipitates from the aqueous Medium off and is filtered off. Finally, the desired product is through Wash with water and then Dry at 45 ° C receive.

Preparation of Polymer MP-06:

In the preparation of polymer MP-06, the procedure is analogous to the preparation of polymer MP-04, with the difference that instead of 31.3 g AM-01 31.1 g AM-03 are used and the mixture of 137.7 g POL-01 solution (40% by weight) and 115 g of NaOAc.3H ₂ O 1000 ml of 1-methoxy-2-propanol instead of 200 ml of 1-methoxy-2-propanol are added.

Preparation of Polymer MP-07:

- Diazonium solution:

A mixture of 17.4 g of AM-01, 80 ml of 1-methoxy-2-propanol and 40 ml of water is stirred and cooled to 5 ° C. Subsequently, 26 ml of concentrated HCl are added and the mixture is cooled to 0 ° C. Thereafter, a solution of 4.7 g of NaNO ₂ in 15 ml of water is added dropwise and then stirred at 0 ° C for 10 minutes.

Phenol polymer solution:

A mixture of 30.0 g of POL-04 dissolved in 125 ml of 1-methoxy-2-propanol and 64 g of NaOAc.3H ₂ O is stirred and cooled to 0 ° C.

The as above diazonium solution will over The phenol polymer solution was added dropwise for 30 minutes, after which 30 Minutes at 0 ° C and stirring is continued for 2 hours at room temperature. There are 50 ml of 1-methoxy-2-propanol and 50 ml of N, N-dimethylacetamide added to the precipitated product to solve. The resulting mixture is then allowed to soak for 30 minutes constant stir added to 3 liters of ice water. The polymer precipitates from the aqueous Medium off and is filtered off. Finally, the desired product by washing with water and subsequent drying at 45 ° C.

Preparation of Polymer MP-08:

- Diazonium solution:

A mixture of 17.4 g of AM-01, 80 ml of 1-methoxy-2-propanol and 40 ml of water is stirred and cooled to 5 ° C. Subsequently, 26 ml of concentrated HCl are added and the mixture is cooled to 0 ° C. Thereafter, a solution of 4.7 g of NaNO ₂ in 15 ml of water is added dropwise and then stirred at 0 ° C for 10 minutes.

Phenol polymer solution:

A mixture of 30.0 g of POL-05 dissolved in 125 ml of 1-methoxy-2-propanol and 64 g of NaOAc.3H ₂ O is stirred and cooled to 0 ° C.

The as above diazonium solution will over The phenol polymer solution was added dropwise for 30 minutes, after which 30 Minutes at 0 ° C and stirring is continued for 2 hours at room temperature. The thus obtained Mixture is then over 30 minutes under constant stir added to 3 liters of ice water. The polymer precipitates from the aqueous Medium off and is filtered off. Finally, the desired product is through Wash with water and then Dry at 45 ° C receive.

Preparation of Polymer MP-09:

at The preparation of polymer MP-09 is analogous to the preparation of Polymer MP-08 proceeded, but with the difference that instead POL-05 30 g phenol polymer POL-06 dissolved in 125 ml 1-methoxy-2-propanol become.

Preparation of Polymer MP-10:

- Diazonium solution:

A mixture of 17.4 g AM-01 and 100 ml acetic acid is stirred and cooled to 5 ° C. Subsequently, 15 ml of concentrated HCl are added and the mixture is cooled to 0 ° C. Thereafter, a solution of 4.7 g of NaNO ₂ in 15 ml of water is added dropwise and then stirred at 0 ° C for 10 minutes.

Phenol polymer solution:

A mixture of 30.6 g of POL-07 dissolved in 200 ml of 1-methoxy-2-propanol, 50 ml of N, N-dimethylacetamide and 68 g of NaOAc.3H ₂ O is stirred and cooled to 0 ° C.

The as above diazonium solution will over The phenol polymer solution was added dropwise for 30 minutes, after which 30 Minutes at 0 ° C and stirring is continued for 2 hours at room temperature. The thus obtained Mixture is then over 30 minutes under constant stir added to 3 liters of ice water. The polymer precipitates from the aqueous Medium off and is filtered off. Finally, the desired product is through Washing with water and a mixture of water and methanol (volume ratio: 7/3) and subsequent Dry at 45 ° C receive.

Preparation of Polymer MP-11:

- Diazonium solution:

A mixture of 27.8 g of AM-01, 260 ml of 1-methoxy-2-propanol and 78 ml of water is stirred and cooled to 5 ° C. Subsequently, 42 ml of concentrated HCl are added and the mixture is cooled to 0 ° C. Thereafter, a solution of 7.6 g of NaNO ₂ in 44 ml of water is added dropwise and then stirred at 0 ° C for 10 minutes.

Phenol polymer solution:

A mixture of 49.0 g of POL-08 dissolved in 280 ml of N, N-dimethylacetamide and 102 g of NaOAc.3H ₂ O is stirred and cooled to 0 ° C.

The as above diazonium solution will over The phenol polymer solution was added dropwise for 60 minutes, after which 30 Minutes at 0 ° C and stirring is continued for 2 hours at room temperature. The thus obtained Mixture is then over 30 minutes under constant stir added to 3.5 liters of ice water. The polymer precipitates from the aqueous Medium off and is filtered off. Finally, the desired product is through Wash with water and then Dry at 45 ° C receive.

Preparation of Polymer MP-12:

at the preparation of polymer MP-12 is analogous to the preparation of Polymer MP-11 proceeded, but with the difference that instead POL-08 48 g phenol polymer POL-09 dissolved in 270 ml N, N-dimethylacetamide become.

Preparation of Polymer MP-13:

at The preparation of polymer MP-13 is analogous to the preparation of Polymer MP-11 proceeded, but with the difference that instead POL-08 48 g phenol polymer POL-10 dissolved in 280 ml N, N-dimethylacetamide become.

Preparation of Polymer MP-14:

at The preparation of polymer MP-14 is analogous to the preparation of Polymer MP-11 proceeded, but with the difference that instead POL-08 48 g phenol polymer POL-11 dissolved in 235 ml N, N-dimethylacetamide become.

Preparation of Polymer MP-15:

at The preparation of polymer MP-15 is analogous to the preparation of Polymer MP-04 proceeded, but with the difference that instead AM-01 is a mixture of 13.3 g of AM-07 dissolved in 300 ml of 1-methoxy-2-propanol and 200 ml of water is used.

Preparation of Polymer MP-16:

at The preparation of polymer MP-16 is analogous to the preparation of Polymer MP-05 proceeded, but with the difference that instead AM-01 a mixture of 21.3 g AM-07 dissolved in 480 ml 1-methoxy-2-propanol and 180 ml of water is used.

Preparation of Polymer MP-17:

In the preparation of polymer MP-17 is proceeded analogously to the preparation of polymer MP-03, but with the difference that a mixture of 5.3 g in 120 ml of 1-methoxy-2-propanol dissolved AM-07 and 80 ml of water and a mixture of 125.2 g POL-02 solution (44% by weight), 46 g NaOAc.3H ₂ O and 200 ml 1-methoxy-2-propanol is used.

Preparation of Polymer MP-18:

The preparation of polymer MP-18 is analogous to the preparation of polymer MP-04 procedure, but with the difference that a mixture of 13.3 g in 300 ml of 1-methoxy-2-propanol dissolved AM-07 and 200 ml of water and a mixture of 125.2 g POL-02 solution (44% by weight), 115 g NaOAc.3H ₂ O and 300 ml 1-methoxy-2-propanol is used.

Preparation of Polymer MP-19:

- Diazonium solution:

A mixture of 16.1 g AM-08, 299 ml acetic acid and 25 ml concentrated HCl is stirred at 45 ° C. Once the total amount of AM-08 has been dissolved, the solution is cooled to 5 ° C. Thereafter, 5 ml of concentrated H ₂ SO _{4 are} added and the mixture is further stirred and cooled to 0 ° C. Thereafter, a solution of 9.0 g of NaNO ₂ in 20 ml of water is added dropwise and then stirred at 0 ° C for 20 minutes.

Phenol polymer solution:

A mixture of 137.7 g of POL-01 solution (40% by weight), 68 g of NaOAc.3H ₂ O and 300 ml of 1-methoxy-2-propanol is stirred and cooled to 0 ° C.

The as above diazonium solution will over The phenol polymer solution was added dropwise for 30 minutes, after which 30 Minutes at 0 ° C and 30 minutes at 10 ° C further stirred becomes. The resulting mixture is then allowed to soak for 30 minutes constant stir added to 2.5 liters of ice water. The polymer precipitates from the aqueous Medium off and is filtered off. Finally, the desired product by washing with water and a mixture of water and methanol (Volume ratio: 6/4) and then drying at 45 ° C receive.

Preparation of Polymer MP-20:

- Diazonium solution:

A mixture of 6.6 g AM-10, 65 ml acetic acid and 37.5 ml water is cooled to 15 ° C. Thereafter, 6.2 ml of concentrated HCl are added and the mixture is further cooled to 0 ° C. Thereafter, a solution of 2.8 g of NaNO ₂ in 7 ml of water is added dropwise and then stirred at 0 ° C for 30 minutes.

Phenol polymer solution:

A mixture of 45.9 g POL-01 solution (40% by weight), 40.8 g NaOAc.3H ₂ O and 200 ml 1-methoxy-2-propanol is stirred and cooled to 10 ° C.

The as above diazonium solution will over The phenol polymer solution was added dropwise for 30 minutes, after which 120 Minutes at 15 ° C further stirred becomes. The resulting mixture is then allowed to soak for 30 minutes constant stir added to 2 liters of ice water. The polymer falls out of the aqueous medium off and is filtered off. Finally, the desired product by washing with water and subsequent drying at 45 ° C.

Preparation of Polymer MP-21:

In the preparation of polymer MP-21, the procedure is analogous to the preparation of polymer MP-20, but with the difference that in the preparation of the diazonium salt, a mixture of 5.3 g of AM-10 and 50 ml of acetic acid, 5 ml of concentrated HCl and 2.3 g of NaNO ₂ in 6 ml of water are used and 32.6 g of NaOAc.3H ₂ O are used in the preparation of the phenolic polymer solution instead of the amounts indicated in the preparation of polymer MP-20.

Preparation of Polymer MP-22:

In the preparation of polymer MP-22 is analogous to the preparation of polymer MP-20, except that in the preparation of the diazonium salt, a mixture of 2.6 g of AM-10 and 25 ml of acetic acid, 2.5 ml of concentrated HCl and 1.1 g NaNO ₂ in 3 ml water and 16.3 g NaOAc.3H ₂ O are used in the preparation of the phenolic polymer solution instead of the amounts indicated in the preparation of Polymer MP-20.

Preparation of Polymer MP-23:

In the preparation of polymer MP-23 is analogous to the preparation of polymer MP-20, except that in the preparation of the diazonium salt, a mixture of 1.33 g of AM-10 and 15 ml of acetic acid, 1.3 ml of concentrated HCl and 0.57 g of NaNO ₂ in 2 ml of water and used in preparing the phenolic polymer solution instead of the amounts indicated in the preparation of polymer MP-20 8.2 g NaOAc.3H ₂ O.

Preparation of Polymer MP-28:

a) first modification reaction on the Phenolic polymer:

- Diazonium solution:

A mixture of 27.9 g AM-01, 240 ml 1-methoxy-2-propanol and 60 ml water is stirred and cooled to 5 ° C. Thereafter, 42 ml of concentrated HCl are added and the mixture is cooled to 0 ° C. Thereafter, a solution of 7.6 g of NaNO ₂ in 30 ml of water is added dropwise and then stirred at 0 ° C for 20 minutes.

Phenol polymer solution:

A mixture of 306 g POL-01 solution (40% by weight), 102 g NaOAc.3H ₂ O and 200 ml 1-methoxy-2-propanol is stirred and cooled to 0 ° C.

The as above diazonium solution will over The phenol polymer solution was added dropwise for 60 minutes, after which 30 Minutes at 0 ° C and stirring is continued for 2 hours at room temperature. The thus obtained Mixture is then over 30 minutes under constant stir added to 15 liters of ice water. The polymer precipitates from the aqueous Medium off and is filtered off. Finally, the desired product is through Wash with water and then dry at 45 ° C receive.

a) second modification reaction on the First modified phenolic polymer:

- Diazonium solution:

A mixture of 2.36 g of AM-07, 30 ml of 1-methoxy-2-propanol and 20 ml of water is stirred and cooled to 5 ° C. Thereafter, 8.4 ml of concentrated HCl are added and the mixture is cooled to 0 ° C. Thereafter, a solution of 1.52 g of NaNO ₂ in 4 ml of water is added dropwise and then stirred at 0 ° C for 15 minutes.

- Solution of the First modified phenolic polymer:

A mixture of 30.2 g of the first modified phenolic polymer dissolved in 200 g of 1-methoxy-2-propanol and 20.4 g of NaOAc.3H ₂ O is stirred and cooled to 0 ° C.

The as above diazonium solution will over 30 minutes of the solution of the first modified phenolic polymer was added dropwise, followed by 30 minutes at 0 ° C and stirring is continued for 2 hours at room temperature. The thus obtained Reaction mixture is added to 200 ml of acetone, after which the reaction mixture is filtered. The resulting filtrate is then over 60 minutes away under constant Stir too 3 liters of ice water. The polymer precipitates from the aqueous Medium off and is filtered off. Finally, the desired product by washing with water and subsequent drying at 45 ° C.

Preparation of Polymer MP-29:

- Diazonium solution:

One Mixture of 13.9 g AM-01, 5.9 g AM-07, 200 ml 1-methoxy-2-propanol and 100 ml of water is stirred and at 5 ° C cooled.

Thereafter, 41 ml of concentrated HCl are added and the mixture is cooled to 0 ° C. Thereafter, a solution of 7.6 g of NaNO ₂ in 20 ml of water is added dropwise and then stirred at 0 ° C for 30 minutes.

Phenol polymer solution:

A mixture of 153 g of POL-01 solution (40% by weight), 102 g of NaOAc.3H ₂ O and 200 ml of 1-methoxy-2-propanol is stirred and cooled to 0 ° C.

The as above diazonium solution will over The phenol polymer solution was added dropwise for 60 minutes, after which 30 Minutes at 0 ° C and stirring is continued for 2 hours at room temperature. The thus obtained Mixture is then over 60 minutes under constant stir added to 5 liters of ice water. The polymer precipitates from the aqueous Medium off and is filtered off. Finally, the desired product is through Wash with water and then Dry at 45 ° C receive.

exam 1:

Preparation of the coating:

• – 86,55 g Dowanol PM,
• – 464,64 g Methylethylketon,
• – 101,28 g einer Lösung des Infrarot-Farbstoffes IR-1 in einem Verhältnis von 2 Gew.-% in Dowanol PM,
• – 144,70 g einer Lösung des Kontrastfarbstoffes CD-1 in einem Verhältnis von 1 Gew.-% in Dowanol PM,
• – 159,14 g einer Lösung von Tego Glide 410 in einem Verhältnis von 1 Gew.-% in Dowanol PM,
• – 159,14 g einer Lösung eines Phenolpolymers (vgl. Tabellen 1 bis 4) in einem Verhältnis von 40 Gew.-% in Dowanol PM und
• – 3,18 g 3,4,5-Trimethoxyzimtsäure.

A coating solution is prepared by adding the following ingredients:

• - 86.55 g Dowanol PM,
• 464.64 g of methyl ethyl ketone,
• 101.28 g of a solution of the infrared dye IR-1 in a ratio of 2% by weight in Dowanol PM,
• 144.70 g of a solution of the contrast dye CD-1 in a ratio of 1% by weight in Dowanol PM,
• 159.14 g of a solution of Tego Glide 410 in a ratio of 1% by weight in Dowanol PM,
• 159.14 g of a solution of a phenolic polymer (see Tables 1 to 4) in a ratio of 40% by weight in Dowanol PM and
• 3.18 g of 3,4,5-trimethoxycinnamic acid.

The coating solution is in a wet layer thickness of 20 μm on an electrochemically roughened and anodized aluminum substrate followed by drying the coating for 1 minute at 130 ° C becomes.

• – Prüflösung 1: 50 gew.-%ige wässrige Isopropanollösung,
• – Prüflösung 2: EMERALD PREMIUM MXEH, im Handel erhältlich durch ANCHOR, und
• – Prüflösung 3: ANCHOR AQUA AYDE, im Handel erhältlich durch ANCHOR.

To measure the chemical resistance, 3 different solutions are used:

• Test solution 1: 50% by weight aqueous isopropanol solution,
• Test solution 2: EMERALD PREMIUM MXEH, commercially available from ANCHOR, and
• Test solution 3: ANCHOR AQUA AYDE, commercially available from ANCHOR.

• 0: kein Angriff,
• 1: geänderter Glanz der Beschichtungsoberfläche,
• 2: beschränkter Angriff der Beschichtung (Abnahme der Stärke),
• 3: erheblicher Angriff der Beschichtung,
• 4: völlig gelöste Beschichtung.

To test the chemical resistance, 40 μl droplets of the three test solutions are applied to different areas of the coating. After 3 minutes, the droplet is wiped off the coating using a cotton swab. The extent to which each test solution attacks the coating is visually evaluated according to the following scale:

• 0: no attack,
• 1: changed gloss of the coating surface,
• 2: limited attack of the coating (decrease in strength),
• 3: considerable attack of the coating,
• 4: completely dissolved coating.

• * VB: vergleichendes Beispiel.

The higher the rating, the lower the chemical resistance of the coating. The results of the 3 test solutions on each coating are summarized in Tables 1 to 4. The tables also list data relating to the type of phenolic polymer used in the modification reaction, the type of modifying reagent and the degree of modification (in mol%), and the MP number of the polymer produced. Table 1: Example number Type phenolic polymer Type of reagent Modif. degree (mol%) MP no. of the polymer produced INSPECTION 1 Test solution 1 INSPECTION 1 Test solution 2 VB * 1 POL-01 - - - 4 4 Ex. 1 POL-01 AM-01 2.5 MP-01 3 3 Ex. 2 POL-01 AM-01 5 MP-02 2 2 Ex. 3 POL-01 AM-01 10 MP-03 2 2 Ex. 4 POL-01 AM-01 25 MP-04 1 1 Ex. 5 POL-01 AM-01 40 MP-05 1 1 Ex. 6 POL-01 AM-03 25 MP-06 1 1

• * VB: comparative example.

• * VB: vergleichendes Beispiel.

The examples in Table 1 clearly show that the polymers modified according to the invention produce a substantial increase in the chemical resistance of the coating compared to the unmodified polymer. Table 2: Example number Type phenolic polymer Type of reagent Modif. degree (mol%) MP no. of the polymer produced INSPECTION 1 Test solution 1 INSPECTION 1 Test solution 3 VB * 2 POL-04 - - - 4 4 Ex. 7 POL-04 AM-01 25 MP-07 2 1 VB * 3 POL-05 - - - 4 4 Ex. 8 POL-05 AM-01 25 MP-08 2 1 VB * 4 POL-06 - - - 4 4 Ex. 9 POL-06 AM-01 25 MP-09 2 1 VB * 5 POL-07 - - - 4 4 Ex. 10 POL-07 AM-01 25 MP-10 2 1 VB * 6 POL-08 - - - 4 4 Ex. 11 POL-08 AM-01 25 MP-11 2 1 VB * 7 POL-09 - - - 4 4 Ex. 12 POL-09 AM-01 25 MP-12 2 2 VB * 8 POL-10 - - - 4 4 Ex. 13 POL-10 AM-01 25 MP-13 2 1 VB * 9 POL-11 - - - 4 4 Ex. 14 POL-11 AM-01 25 MP-14 2 1

• * VB: comparative example.

• * VB: vergleichendes Beispiel.

The examples in Table 2 clearly show that other polymers modified according to the invention cause a significant increase in the chemical resistance of the coating compared to the unmodified polymers. Table 3: Example number Type phenolic polymer Type of reagent Modif. degree (mol%) MP no. of the polymer produced INSPECTION 1 Test solution 1 INSPECTION 1 Test solution 3 VB * 10 POL-01 - - - 4 4 Ex. 15 POL-01 AM-07 25 MP-15 1 2 Ex. 16 POL-01 AM-07 40 MP-16 0 1 VB * 11 POL-02 - - - 4 4 Ex. 17 POL-02 AM 07 10 MP-17 3 3 Ex. 18 POL-02 AM-07 25 MP-18 1 1 Ex. 19 POL-01 AM-08 25 MP-19 2 3 Ex. 20 POL-01 AM-10 25 MP-20 1 1

• * VB: comparative example.

The examples in Table 3 clearly show that the polymers modified according to the invention with different types of azoaryl groups in different amounts cause a substantial increase in the chemical resistance of the coating. Table 4: Example number Type phenolic polymer Type of reagent Modif. degree (mol%) MP no. of the prepared polymer INSPECTION 1 Test solution 1 INSPECTION 1 Test solution 3 Ex. 26 POL-01 AM-01 + AM-07 10 10 MP-28 1 2 Ex. 27 POL-01 Mixture AM-01 + AM-07 10 10 MP-29 1 2

The Examples in Table 4 clearly show that according to the invention with a Combination of 2 different types of Azoarylgruppen modified Polymers a significant increase in chemical resistance cause the coating.

exam 2:

Preparation of the coating:

• – 313,45 g Dowanol PM,
• – 482,40 g Methylethylketon,
• – 50,64 g einer Lösung des Infrarot-Farbstoffes IR-1 in einem Verhältnis von 2 Gew.-% in Dowanol PM,
• – 72,35 g einer Lösung des Kontrastfarbstoffes CD-1 in einem Verhältnis von 1 Gew.-% in Dowanol PM,
• – 79,57 g einer Lösung eines Phenolpolymers (vgl. Tabelle 5) in einem Verhältnis von 40 Gew.-% in Dowanol PM und
• – 1,59 g 3,4,5-Trimethoxyzimtsäure.

A coating solution is prepared by adding the following ingredients:

• - 313.45 g Dowanol PM,
• 482.40 g of methyl ethyl ketone,
• 50.64 g of a solution of the infrared dye IR-1 in a ratio of 2% by weight in Dowanol PM,
• 72.35 g of a solution of the contrast dye CD-1 in a ratio of 1% by weight in Dowanol PM,
• - 79.57 g of a solution of a phenolic polymer (see Table 5) in a ratio of 40 wt .-% in Dowanol PM and
• - 1.59 g of 3,4,5-trimethoxycinnamic acid.

The half the surface of an electrochemically roughened and anodized aluminum substrate in a wet layer thickness of 10 μm with the above solution coated. The sample is dried for 1 minute at 130 ° C and with OZASOL RC515, one available from AGFA Product, gummed to the non-coated part of the aluminum substrate to protect.

Print:

• * VB = vergleichendes Beispiel.

The plate is clamped in an ABDick 360 press. The printing ink used is the printing ink "K + E 800 Skinnex Black" commercially available from BASF, and the "Emerald Premium MXEH" commercially available from ANCHOR as dampening solution. Pad strength is determined based on the maximum number of prints that can be printed on the print area without any significant signs of wear. The overlay strength test is stopped after 100,000 copies. The run lengths achieved are listed in Table 5. Table 5 also lists data on the phenolic polymer type used in the modification reaction, the type of modifying reagent and the degree of modification (in mol%), and the MP number of the polymer produced. Table 5: Example number Type phenolic polymer Type of reagent Modif. degree (mol%) MP no. of the polymer produced CHECK 2 run length VB * 12 POL-01 - - - 25,000 Ex. 28 POL-01 AM-01 2.5 MP-01 43,000 Ex. 29 POL-01 AM-01 5 MP-02 45,000 Ex. 30 POL-01 AM-01 10 MP-03 75,000 Ex. 31 POL-01 AM-01 25 MP-04 73,000 Ex. 32 POL-01 AM-01 40 MP-05 64,000 Ex. 33 POL-01 AM-10 25 MP-20 > 100,000

• * VB = comparative example.

The Examples in Table 5 clearly show that the invention modified Opposite polymers the unmodified Polymer cause a significant increase in the coating strength of the coating.

exam 3:

Preparation of the coating:

• – 209,1 g Tetrahydrofuran,
• – 105 g einer Lösung eines Phenolpolymers (vgl. Tabelle 6) in einem Verhältnis von 40 Gew.-% in Dowanol PM,
• – 327 g Dowanol PM,
• – 266 g Methylethylketon,
• – 1,51 g des Infrarot-Farbstoffes IR-1,
• – 54 g einer 1 gew.-%igen Lösung von Basonyl Blue 640, im Handel erhältlich durch BASF, in Dowanol PM,
• – 32,4 g einer Lösung von Tego Glide 410 in einem Verhältnis von 1 Gew.-% in Dowanol PM (Bemerkung: in Beispiel 39 werden 8,5 g statt 32,4 g dieser Lösung verwendet) und
• – eine in Tabelle 6 angegebene Grammmenge 3,4,5-Trimethoxyzimtsäure (im Nachstehenden als TMCA bezeichnet).

A coating solution is prepared by adding the following ingredients:

• 209.1 g of tetrahydrofuran,
• 105 g of a solution of a phenolic polymer (see Table 6) in a ratio of 40% by weight in Dowanol PM,
• - 327 grams of Dowanol PM,
• 266 g of methyl ethyl ketone,
• 1.51 g of the infrared dye IR-1,
• 54 g of a 1% by weight solution of Basonyl Blue 640, commercially available from BASF, in Dowanol PM,
• 32.4 g of a solution of Tego Glide 410 in a ratio of 1% by weight in Dowanol PM (note: in Example 39, 8.5 g instead of 32.4 g of this solution are used) and
• A gram amount of 3,4,5-trimethoxycinnamic acid (hereinafter referred to as TMCA) given in Table 6.

The coating solution is in a coating plant at a speed of 8 m / min. and a drying temperature of 130 ° C in a wet layer thickness of 26 μm up an electrochemically roughened and anodized aluminum substrate applied.

Exposure:

The printing plate precursors are exposed at the energy density (in mJ / cm ² ) indicated in Table 6 on a CreoScitex Trendsetter 3244.

Development:

The imagewise exposed Printing plate precursors are in one at a speed of 0.96 m / min. and a temperature of 25 ° C Agfa Autolith T-processor using the TD5000 developer commercially available from Agfa and the commercially available RC795 gum solution from Agfa.

Print:

• * VB = vergleichendes Beispiel,
• ** BW = Belichtungswert.

The developed plates are clamped as a printing master in a Sakurai Oliver 52 printing press. The ink used is K + E 800 Skinnex Black, commercially available from BASF, and a 4% Emerald Premium MXEH solution as dampening solution. The printing cycle of each plate is 100,000 Copies (100 K), the run length being determined as shown in Table 6. Table 6: Example number Type phenolic polymer Type of reagent Modif. Degree (mol%) MP no. of the polymer produced TMCA (g) BW ** (mJ / cm ² ) EXAMINATION 3 editions height VB * 13 POL-01 - - - 5.40 160 50K Ex. 36 POL-01 AM-01 5 MP-02 1.95 300 > 100K Ex. 37 POL-01 AM-10 5 MP-23 4.32 232 > 100K Ex. 38 POL-01 AM-10 10 MP-22 4.11 264 > 100K Ex. 39 POL-01 AM-10 20 MP-21 5.30 291 > 100K

• * VB = comparative example,
• ** BW = exposure value.

The Examples in Table 6 clearly show that they are modified according to the invention Polymers a significant increase in the run resistance of the printing plate cause.

exam 4:

Preparation of the coating:

It the same materials as described in test 3 are used.

• – das Gewicht "A" jeder Probe wird gemessen,
• – diese Proben werden 3 Minuten lang in Prüflösung 1 von Prüfung 1 eingetaucht und anschließend mit Wasser gespült und getrocknet,
• – das Gewicht "B" jeder Probe wird gemessen,
• – die wärmeempfindliche Beschichtung jeder Probe wird durch Lösen mit Methylethylketon abgelöst (bei unvollständiger Entfernung der Beschichtung können andere geeignete Lösungsmittel, wie Aceton, Tetrahydrofuran, Dowanol PM, Methanol oder Butyrolacton, verwendet werden),
• – diese Proben werden mit Wasser gespült und getrocknet,
• – das Gewicht "C" jeder Probe wird gemessen und
• – der prozentuale Gewichtsverlust jeder Probe wird nach folgender Formel berechnet: (A – B) × 100%/(A – C).

The percentage weight loss test is carried out by the following procedure on a 10 × 10 cm sample of each of the above-described printing plate precursors:

• The weight "A" of each sample is measured
• - these samples are immersed for 3 minutes in test solution 1 of test 1 and then rinsed with water and dried,
• The weight "B" of each sample is measured
• The heat-sensitive coating of each sample is removed by dissolution with methyl ethyl ketone (if the coating is not completely removed, other suitable solvents, such as acetone, tetrahydrofuran, Dowanol PM, methanol or butyrolactone, may be used),
• These samples are rinsed with water and dried,
• - the weight "C" of each sample is measured and
• - the percentage weight loss of each sample is calculated according to the following formula: (A - B) × 100% / (A - C).

The results are listed in Table 7. Table 7: Example number Material type: Same type as with Weight "A" Weight "B" Weight "C" TEST 4 per cent. weight loss See Example 14 See Example 13 7.5276 7.5222 7.5165 49 Example 40 Example 36 7.3785 7.3785 7.3683 0 Example 41 Example 37 7.3169 7.3163 7.3064 6 Example 42 Example 38 7.3655 7.3647 7.3548 7 Example 43 Example 39 7.3816 7.3813 7.3720 3

The examples in Table 7 show that printing plate precursors having in their coating one of these According to the invention, containing different types of azoaryl groups in different amounts modified polymers have a very low percentage weight loss, indicating a significant increase in chemical resistance. All the other examples 1 to 39 also show a weight loss of less than 45%.

exam 5:

Preparation of the coating:

Comparative Example 15 and example of the invention 44 are described analogously Comparative Example 13 and Example 39 (see examination 3 and Table 6).

• – Prüflösung 4: METER-X ist ein im Handel durch ABC CHEMICAL CORP. LTD. erhältlicher Reiniger für Dosier- und Feuchtwalzen,
• – Prüflösung 5: WASH R-228 ist ein im Handel durch ANCHOR erhältlicher Gummituch- und Druckwalzenreiniger.

The measurement of the chemical resistance is carried out analogously to test 1, but with the difference that instead of test solution 1, 2 or 3 test solution 4 and test solution 5 are used:

• Test solution 4: METER-X is commercially available from ABC CHEMICAL CORP. LTD. available cleaner for dosing and dampening rollers,
• Test Solution 5: WASH R-228 is a blanket and pressure roller cleaner commercially available from ANCHOR.

The evaluation is carried out according to the same scale as in Test 1 and the results are listed in Table 8. Table 8: Example number Material type: Same type as with Test 5 Test solution 4 Test 5 Test solution 5 Comparative Example 15 Comparative Example 13 4 2 Example 44 Example 39 2 1

example 44 in Table 8 shows that a coating based on a modified polymer according to the invention a significant increase in chemical resistance to printing chemicals results.

exam 6:

Preparation of the coating:

• – 10,12 g Tetrahydrofuran,
• – 5,54 g einer Lösung eines Phenolpolymers (vgl. Tabelle 9) in einem Verhältnis von 40 Gew.-% in Dowanol PM,
• – 19,7 g Dowanol PM,
• – 12,9 g Methylethylketon,
• – 0,12 g des Infrarot-Farbstoffes IR-1,
• – 1,16 g Cymel 303, im Handel erhältlich durch DYNO CYTEC und
• – 0,3 g 3,4,5-Trimethoxyzimtsäure.

A coating solution is prepared by adding the following ingredients:

• 10.12 g of tetrahydrofuran,
• 5.54 g of a solution of a phenolic polymer (see Table 9) in a ratio of 40% by weight in Dowanol PM,
• - 19.7 g Dowanol PM,
• 12.9 g of methyl ethyl ketone,
• 0.12 g of the infrared dye IR-1,
• - 1.16 g Cymel 303, commercially available from DYNO CYTEC and
• - 0.3 g of 3,4,5-trimethoxycinnamic acid.

The coating solution is in a wet layer thickness of 16 μm on an electrochemically roughened and anodized aluminum substrate applied and then 5 minutes at 90 ° C dried.

Exposure and preheating:

The printing plate precursors are exposed at an energy density of 300 mJ / cm ² on a CreoScitex Trendsetter 3244 and then preheated for 1 minute at 110 ° C.

Development:

The imagewise exposed and preheated printing plate precursors are developed with the New Unideo developer commercially available from AGFA to remove the non-image areas. After flushing with Water will get the finished printing plate.

• * VB: vergleichendes Beispiel.

For the measurement of the chemical resistance, test 1 is used analogously. The results for the test solutions on each coating are listed in Table 9. Also listed in this table are data on the phenolic polymer type used in the modification reaction, the type of modifying reagent and the degree of modification (in mol%), and the MP number of the polymer produced. Table 9: Example number Type phenolic polymer Type of reagent Modif. degree (mol%) MP no. of the polymer produced INSPECTION 6 Test solution 2 INSPECTION 6 Test solution 3 VB * 16 POL-01 - - - 4 2 Ex. 45 POL-01 AM-10 20 MP-21 0 0 Ex. 46 POL-01 AM-10 25 MP-20 1 0

• * VB: comparative example.

Comment: the lower chemical resistance value for the negative working comparative example 16 is based on the fact that the image areas of this negative-working plate in contrast are linked to the positive working examples.

The Examples 45 and 46 in Table 9 clearly show that negative working Coatings containing the polymers modified according to the invention, give a substantial increase in chemical resistance.

Claims (18)

A heat sensitive lithographic printing plate precursor having a support having a hydrophilic surface and one on the hydrophilic surface attached oleophilic coating, the coating - one IR absorber and - one Containing polymer having a phenolic monomer unit, wherein the phenyl group the phenolic monomer unit by a group according to the structure -N = N-Q, in which the -N = N group is covalently attached to a carbon atom the phenyl group is bonded and Q is an aromatic group, is substituted. A lithographic printing plate precursor according to claim 1, characterized in that Q is a group having at least one Heteroatom is. A lithographic printing plate precursor according to claim 2, characterized in that the heteroatom is a nitrogen atom, is an oxygen atom or a sulfur atom. Lithographic printing plate precursor according to claims 1, 2 or 3, characterized in that Q corresponds to the structure -A- (T) _n , in which A is a monocyclic, 5-membered or 6-membered aromatic group or a 5-membered or 6-membered In other words, n is an integer between 0 and the maximum number of positions present on the aromatic group A, and each T group is -SO ₂ -NH-R ¹ , -NH-SO ₂ -R ⁴ , -CO-NR ¹ -R ² , -NR ¹ -CO-R ⁴ , -NR ¹ -CO-NR ² -R ³ , -NR ¹ -CS-NR ² -R ³ , -NR ¹ -CO-OR ¹ , -O-CO-NR ¹ -R ² , -O-CO-R ⁴ , -CO-OR ² , -CO-R ³ , -SO ₃ -R ¹ , -O-SO ₂ - R ⁴ , -SO ₂ -R ¹ , -SO-R ⁴ , -P (= O) (- OR ¹ ) (- OR ² ), -OP (= O) (- OR ¹ ) (- OR ² ), -NR ¹ -R ² , -OR ² , -SR ² , -N = NR ⁴ , -CN, -NO ₂ , halide or -MR ¹ , where M is a divalent linking group having 1 to 8 carbon atoms, wherein R ¹ , R ² and R ³ are each independently a hydrogen atom or a given optionally substituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, heterocyclic group, aryl group, heteroaryl group, aralkyl group or heteroaralkyl group, wherein R ⁴ and R ^{5 represents} an optionally substituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, heterocyclic group, aryl group, heteroaryl group, aralkyl group or heteroaralkyl group . or wherein at least two groups from the series of R ¹ to R ⁵ together represent the atoms needed to form a cyclic structure. Lithographic printing plate precursor according to one of claims 1 to 3, characterized in that the -N = NQ group corresponds to the formula:

in which: X is CD ³ , ND ⁴ or N, Y is the atom required to form a 5-membered or 6-membered aromatic ring, said atoms being selected from the group consisting of CD ³ , ND ⁴ , N, S and O. wherein D ¹ , D ² and D ^{3 are} a hydrogen atom, an optionally substituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, heterocyclic group, aryl group, heteroaryl group, aralkyl group or heteroaralkyl group, -SO ₂ -NH-D ⁵ , -NH-SO ₂ -D ⁷ , -CO-NR ⁵ -D ⁶ , -ND ⁵ -CO-D ⁷ , -O-CO-D ⁷ , -CO-OD ⁵ , -CO-D ⁵ , -SO ₃ -D ⁵ , -SO ₂ -D ⁵ , -SO-D ⁷ , -P (= O) (- OD ⁵ ) (- OD ⁶ ), -ND ⁵ -D ⁶ , -OD ⁵ , -SD ⁵ , -CN, -NO ₂ , a halogen atom or -MD ⁵ , wherein M represents a divalent linking group having 1 to 8 carbon atoms, wherein D ⁴ , D ⁵ and D ⁶ each independently represent a hydrogen atom or an optionally substituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, heterocyclic Group, aryl group, Heteroaryl group, aralkyl group or heteroaralkyl group, wherein D ^{7 represents} an optionally substituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, heterocyclic group, aryl group, heteroaryl group, aralkyl group or heteroaralkyl group, or wherein at least two groups from the series of D ¹ to D ⁷ together that to Formation of a cyclic structure needed atoms mean. Lithographic printing plate precursor according to one of claims 1 to 3, characterized in that the -N = NQ group corresponds to the formula:

in which: Z ¹ and Z ² are each, independently of one another, CE ¹ or N, where E ^{1 is} a hydrogen atom or an optionally substituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, heterocyclic group, aryl group, heteroaryl group, aralkyl group or heteroaralkyl group, p 0, 1 , 2, 3 or 4, r is 0, 1, 2 or 3, E ² and E ³ are each independently hydrogen, optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, heterocyclic, aryl, heteroaryl, aralkyl or heteroaralkyl , -SO ₂ -NH-E ⁴ , -NH-SO ₂ -E ⁶ , -CO-NE ⁴ -E ⁵ , -NE ⁴ -CO-E ⁶ , -O-CO-E ⁶ , -CO-OE ⁴ , -CO-e ^4, -SO ₃ -E ^4, -SO ₂ -E ^4, -SO-e ^6, -P (= O) (- ⁴ OE) (- OE ^5), -NE ⁴ -E ⁵ , -OE ⁴ , -SE ⁴ , -CN, -NO ₂ , a halogen atom or -ME ⁴ , wherein M represents a divalent linking group having 1 to 8 carbon atoms, represent, wherein E ⁴ and E ⁵ are each independently a Wasse R represents an oxygen atom or an optionally substituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, heterocyclic group, aryl group, heteroaryl group, aralkyl group or heteroaralkyl group, wherein E ^{6 represents} an optionally substituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, heterocyclic group, aryl group, heteroaryl group, aralkyl group or heteroaralkyl group , or wherein at least two groups from the series of E ¹ to E ⁶ together represent the atoms needed to form a cyclic structure. Lithographic printing plate precursor according to one of claims 1 to 3, characterized in that the -N = NQ group corresponds to the formula:

in which: q is 0, 1, 2, 3, 4 or 5, F ^{1 is} a hydrogen atom or an optionally substituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, heterocyclic group, aryl group, heteroaryl group, aralkyl group or heteroaralkyl group, -SO ₂ -NH- F ² , -NH-SO ₂ -F 4, -CO-NF ² -F ³ , -NF ² -CO-F ⁴ , -O-CO-F ⁴ , -CO-OF ² , -CO-F ² , - SO ₃ -F ^2, -SO ₂ -F ^2, -SO-F ^4, -P (= O) (- OF ²⁾ (- OF ^3), -NF ² -F ^3, -OF ² -SF ² , -CN, -NO ₂ , a halogen atom or -MF ² , where M is a divalent linking group having 1 to 8 carbon atoms, where F ² and F ³ are each independently a hydrogen atom or an optionally substituted alkyl group, alkenyl group, alkynyl group, Cycloalkyl group, heterocyclic group, aryl group, heteroaryl group, aralkyl group or heteroaralkyl group, wherein F ^{4 represents} an optionally substituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, heterocyclic group, aryl group, heteroa or at least two groups from the series of F ¹ to F ⁴ together represent the atoms required for the formation of a cyclic structure. Lithographic printing plate precursor according to one of claims 1 to 3, characterized in that the -N = NQ group corresponds to the formula:

in which: p is 0, 1, 2, 3 or 4, G ^{1 represents} a hydrogen atom, an optionally substituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, heterocyclic group, aryl group, heteroaryl group, aralkyl group or heteroaralkyl group, -SO ₂ -NH-G ² , -NH-SO ₂ -G ⁴ , -CO-NG ² -G ³ , -NG ² -CO-G ⁴ , -O-CO-G ⁴ , -CO-OG ² , -CO-G ² , -SO ₃ -G ² , -SO ₂ -G ² , -SO-G ⁴ , -P (= O) (- OG ² ) (- OG ³ ), -NG ² -G ³ , -OG ² , -SG ² , -CN, -NO ₂ , a halogen atom or -MG ² , wherein M represents a divalent linking group having 1 to 8 carbon atoms, Z ^{3 represents} 0, S or NG ⁵ , wherein G ² , G ³ and G ⁵ independently of each other represents a hydrogen atom or an optionally substituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, heterocyclic group, aryl group, heteroaryl group, aralkyl group or heteroaralkyl group, wherein G ^{4 represents} an optionally substituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, heterocyclic heo group, aryl group, heteroaryl group, aralkyl group or heteroaralkyl group, or wherein at least two groups from the series of G ¹ to G ⁵ together represent the atoms needed to form a cyclic structure. Lithographic printing plate precursor according to one of claims 1 to 3, characterized in that the -N = NQ group corresponds to the formula:

in which: r is 0, 1, 2 or 3, U ^{1 is} a hydrogen atom, an optionally substituted alkyl group, alkenyl group, alkynyl group, cyclo alkyl group, heterocyclic group, aryl group, heteroaryl group, aralkyl group or heteroaralkyl group, -SO ₂ -NH-U ² , -NH-SO ₂ -U ⁴ , -CO-NU ² -U ³ , -NU ² -CO-U ⁴ , - O-CO-U ⁴ , -CO-OU ² , -CO-U ² , -SO ₃ -U ² , -SO ₂ -U ² , -SO-U ⁴ , -P (= O) (- OU ² ) (-OU ³ ), -NU ² -U ³ , -OU ² , -SU ² , -CN, -NO ₂ , a halogen atom or -MU ² , wherein M represents a divalent linking group having 1 to 8 carbon atoms, wherein Each of U ² , U ³ , U ⁵ and U ⁶ independently represents a hydrogen atom or an optionally substituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, heterocyclic group, aryl group, heteroaryl group, aralkyl group or heteroaralkyl group, where U ^{4 is} an optionally substituted alkyl group, alkenyl group, Alkynyl group, cycloalkyl group, heterocyclic group, aryl group, heteroaryl group, aralkyl group or heteroaralkyl group, or wherein at least two groups from the series of U ¹ to U ⁴ together the atoms required to form a cyclic structure or wherein U ⁵ and U ⁶ together represent the atoms needed to form a cyclic structure. Lithographic printing plate precursor according to one of claims 1 to 3, characterized in that the -N = NQ group corresponds to the formula:

in which: r is 0, 1, 2 or 3, p is 0, 1, 2, 3 or 4, V ¹ and V ² are each independently a hydrogen atom, an optionally substituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, heterocyclic group, Aryl group, heteroaryl group, aralkyl group or heteroaralkyl group, -SO ₂ -NH-V ³ , -NH-SO ₂ -V ⁵ , -CO-NV ³ -V ⁴ , -NV ³ -CO-V ⁵ , -O-CO-V ⁵ , -CO-OV ³ , -CO-V ³ , -SO ₃ -V ³ , -SO ₂ -V ³ , -SO-V ⁵ , -P (= O) (- OV ³ ) (- OV ⁴ ) , -NV ³ -V ⁴ , -OV ³ , -SV ³ , -CN, -NO ₂ , a halogen atom or -MV ³ , wherein M represents a divalent linking group having 1 to 8 carbon atoms, wherein V ³ and V ⁴ each independently represents a hydrogen atom or an optionally substituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, heterocyclic group, aryl group, heteroaryl group, aralkyl group or heteroaralkyl group, wherein V ^{5 represents} an optionally substituted alkyl group, alkenyl group, alkynyl group , Cycloalkyl group, heterocyclic group, aryl group, heteroaryl group, aralkyl group or heteroaralkyl group, or wherein at least two groups from the series of V ¹ to V ⁵ together represent the atoms needed to form a cyclic structure. Lithographic printing plate precursor according to one of claims 1 to 3, characterized in that the -N = NQ group corresponds to the formula:

in which: r is 0, 1, 2 or 3, W ^{1 is} a hydrogen atom, an optionally substituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, heterocyclic group, aryl group, heteroaryl group, aralkyl group or heteroaralkyl group, -SO ₂ -NH-W ² , - NH-SO ₂ -W ⁴ , -CO-NW ² -W ³ , -NU ² -CO-W ⁴ , -O-CO-W ⁴ , -CO-OW ² , -CO-W ² , -SO ₃ - W ² , -SO ₂ -W ² , -SO-W ⁴ , -P (= O) (- OW ² ) (- OW ³ ), -NW ² -W ³ , -OW ² , -SW ² , -CN , -NO ₂ , a halogen atom or -MW ² , wherein M represents a divalent linking group having 1 to 8 carbon atoms, represents, wherein W ² , W ³ , W ⁵ and W ⁶ each independently represent a hydrogen atom or an optionally substituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, heterocyclic group, aryl group, heteroaryl group, aralkyl group or heteroaralkyl group, wherein W ^{4 represents} an optionally substituted alkyl group, alkenyl group , Alkynyl group, cycloalkyl group, heterocyclic group, aryl group, heteroaryl group, aralkyl group or heteroaralkyl group, or wherein at least two groups from the series of W ¹ to W ⁶ together represent the atoms needed to form a cyclic structure. Lithographic printing plate precursor according to one of claims 1 to 3, characterized in that the -N = NQ group corresponds to one of the following formulas:

Lithographic printing plate precursor according to one of previous claims, characterized in that the polymer has a phenolic monomer unit a novolac, resole or polyvinylphenol. Lithographic printing plate precursor according to one of claims 1 to 13, characterized in that the coating further comprises a Latent Brönsted acid and an acid-crosslinkable Contains connection and the precursor, a negative working lithographic printing plate precursor is. Lithographic printing plate precursor according to one of claims 1 to 13, characterized in that the coating further comprises a dissolution inhibitor contains and the precursor a positive working lithographic printing plate precursor is. A lithographic printing plate precursor according to claim 15, characterized in that the dissolution inhibitor: - an organic Compound is the at least one aromatic group and a hydrogen bond site contains and or - one Polymer or surfactant with siloxane or Perfluoralkyleinheiten is. Use of a polymer with a phenolic monomer unit, wherein the phenyl group of the phenolic monomer unit is replaced by a group corresponding to the structure -N = N-Q, in which the -N = N - group is covalent is bonded to a carbon atom of the phenyl group and Q is a aromatic group is substituted in a coating a positive-working heat-sensitive one lithographic printing plate precursor, the coating further comprising: - one IR absorber and - one dissolution inhibitor contains around the chemical resistance the coating against hydraulic fluids and to increase printing chemicals. Use of a polymer with a phenolic monomer unit, wherein the phenyl group of the phenolic monomer unit is replaced by a group corresponding to the structure -N = N-Q, in which the -N = N - group is covalent is bonded to a carbon atom of the phenyl group and Q is a aromatic group is substituted in a coating a negative-working heat-sensitive lithographic printing plate precursor, the coating further comprising: - one IR absorber, - one Latent Brönsted acid and - an acid-crosslinkable Contains compound around the chemical resistance the coating against hydraulic fluids and to increase printing chemicals.