Positive-working lithographic printing plate precursors
View Patent ↗A positive-working lithographic printing plate precursor has an outermost imageable layer that is present at a dry coverage weight of at least 0.7 g/m 2 and up to and including 1.6 g/m 2 and comprises a primary polymeric binder comprising recurring units of a hydroxyaryl acetal or a hydroxyaryl ester, or recurring units of both a hydroxyaryl acetal and a hydroxyaryl ester. The outermost imageable layer also contains an alkali-soluble secondary vinyl polymer that is not a primary polymeric binder and a non-polymeric polyhydric phenol. These precursors comprise an infrared radiation absorber to make them sensitive and imageable using infrared radiation. After imaging, the precursors can be processed (developed) using an relatively low pH developer such as a silicate- or metasilicate-free developer.
1. A positive-working lithographic printing plate precursor comprising a substrate, and disposed over this substrate, an outermost imageable layer, and the lithographic printing plate precursor further comprising an infrared radiation absorber,
the outermost imageable layer having a dry coating weight of at least 0.7 g/m 2 and up to and including 1.6 g/m 2 , and comprising:
a primary polymeric binder,
an alkali-soluble secondary vinyl polymer that is not a primary polymeric binder, and
a non-polymeric polyhydric phenol,
wherein the primary polymeric binder comprises recurring units from either or both of Structures (Ia) and (Ib) so that the primary polymeric binder comprises at least 15 mol % and up to and including 100 mol % of both types of recurring units:
wherein R and R′ are independently hydrogen or a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, or a halo group,
R 1 is a substituted or unsubstituted hydroxyaryl group wherein the aryl group has 1 to 3 hydroxyl groups on the ring, and
R 2 is a substituted or unsubstituted hydroxyaryl group that is substituted with a cyclic aliphatic or aromatic imide group, and
further that the Structure (Ia) recurring units are present in an amount of at least 10 mol % and up to and including 50 mol % and the Structure (Ib) recurring units are present in an amount of at least 15 mol % and up to and including 70 mol %, based on total recurring units.
2. The precursor of claim 1 wherein the outermost imageable layer has a dry coating weight of at least 1.1 g/m 2 and up to and including 1.5 g/m 2 .
3. The precursor of claim 1 wherein the alkali-soluble secondary vinyl polymer has an acid number of at least 30 mg KOH/g of alkali-soluble secondary vinyl polymer and up to and including 170 mg KOH/g of alkali-soluble secondary vinyl polymer.
4. The precursor of claim 1 wherein the amount of the alkali-soluble secondary vinyl polymer and the amount of the non-polymeric polyhydric phenol in the outermost imageable layer are independently up to and including 10 weight %.
5. The precursor of claim 1 wherein the primary polymeric binder is present in the outermost imageable layer in an amount of at least 50 weight % and up to and including 95 weight %.
6. The precursor of claim 1 wherein the alkali-soluble secondary vinyl polymer is a vinyl phenol copolymer, (meth)acrylic acid copolymer, a polymer that comprises recurring units capable of producing carboxylic acid upon heating or in presence of acid, or a crotonic copolymer.
7. The precursor of claim 1 wherein the polyhydric phenol is selected from the group consisting of quercetin, catechin hydrate, rutin hydrate, Aloin A, gallic acid, chrysin, morin hydrate, and 2,2-bis(3-hydroxy-1,4-naphthoquinone).
8. The precursor of claim 1 comprising an inner imageable layer disposed over the substrate, and the outermost imageable layer is disposed over the inner imageable layer.
9. The precursor of claim 8 comprising the infrared radiation absorber in the inner imageable layer.
10. The precursor of claim 1 wherein:
the outermost imageable layer has a dry coating weight of at least 1.1 g/m 2 and up to and including 1.4 g/m 2 ,
the alkali-soluble secondary vinyl polymer has an acid number of at least 30 mg KOH/g of alkali-soluble secondary vinyl polymer and up to and including 170 mg KOH/g of alkali-soluble secondary vinyl polymer, and is a vinyl phenol copolymer, (meth)acrylic acid copolymer, a polymer that comprises recurring units capable of producing carboxylic acid upon heating or in the presence of acid, or a crotonic copolymer,
the amount of the alkali-soluble secondary vinyl polymer and the amount of the non-polymeric polyhydric phenol in the outermost imageable layer are independently up to and including 10 weight %,
the primary polymeric binder is present in the outermost imageable layer in an amount of at least 50 weight % and up to and including 95 weight %, and
the polyhydric phenol is selected from the group consisting of quercetin, catechin hydrate, rutin hydrate, Aloin A, gallic acid, chrysin, morin hydrate, and 2,2-bis(3-hydroxy-1,4-naphthoquinone).
11. The precursor of claim 10 that further comprises an inner imageable layer disposed over the substrate, and the outermost imageable layer is disposed over the inner imageable layer.
12. The precursor of claim 11 wherein the infrared radiation absorber is present only in the inner imageable layer.
13. The precursor of claim 1 wherein the substrate is an aluminum substrate comprising a hydrophilic surface over which the outermost imageable layer is disposed.
14. A method for preparing a lithographic printing plate, comprising:
imagewise exposing the positive-working lithographic printing plate precursor of claim 1 with infrared radiation to form exposed regions and non-exposed regions in the outermost imageable layer, and
removing the exposed regions of the outermost imageable layer to provide a lithographic printing plate.
15. The method of claim 14 comprising removing the exposed regions off-press using a processing solution.
16. The method of claim 14 comprising imagewise exposing the positive-working lithographic printing plate precursor using a laser and a fluence of at least 40 mJ/cm 2 .
17. The method of claim 14 wherein the lithographic printing plate precursor comprises an inner imageable layer disposed over the substrate, and the outermost imageable layer is disposed over the inner imageable layer.
18. The method of claim 14 comprising removing the exposed regions from the outermost imageable layer using a silicate- and metasilicate-free processing solution.
19. A method for preparing a lithographic printing plate, comprising:
imagewise exposing the positive-working lithographic printing plate precursor of claim 10 with infrared radiation to form exposed regions and non-exposed regions in the outermost imaging layer, and
removing the exposed regions of the outermost imaging layer to provide a lithographic printing plate.
20. The method of claim 19 comprising removing the exposed regions from the outermost imageable layer using a silicate- and metasilicate-free processing solution.