Method of forming a positive image through infrared exposure...

Radiation imagery chemistry: process – composition – or product th – Imaging affecting physical property of radiation sensitive... – Forming nonplanar surface

Reexamination Certificate

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C430S944000

Reexamination Certificate

active

06482577

ABSTRACT:

FIELD OF THE INVENTION
This invention relates to a photosensitive composition and positive-working element that are sensitive to infrared radiation. In particular, this invention relates to positive-working lithographic printing plates.
BACKGROUND OF THE INVENTION
The art of lithographic printing is based upon the immiscibility of oil and water, wherein the oily material or ink is preferentially retained by the image area and the water or fountain solution is preferentially retained by the non-image area. When a suitably prepared surface is moistened with water and an ink is then applied, the background or non-image areas retain the water and repel the ink while the image areas accept the ink and repel the water. The ink on the image areas is then transferred to the surface of a material upon which the image is to be reproduced, such as paper, cloth and other materials. Commonly, the ink is transferred to an intermediate material called the blanket which in turn transfers the ink to the surface of the material upon which the image is to be reproduced.
A widely used type of lithographic printing plate has a light-sensitive coating applied to an aluminum base support. The coating may respond to light by having the portion that is exposed become soluble so that it is removed in the developing process. Such a plate is referred to in the art as a positive-working printing plate. Conversely, when that portion of the coating that is exposed becomes hardened, the plate is referred to as a negative-working plate. In both instances, the image areas remaining are ink-receptive or oleophilic and the non-image areas or background are water-receptive or hydrophilic. The differentiation between image and non-image areas is made in the exposure process where a film is applied to the plate with a vacuum to insure good contact. The plate is then exposed to a light source, a portion of which is composed of UV radiation. In the instance of negative-working plates, the areas on the film corresponding to the image areas are clear, allowing light to harden the image area coating, while the areas on the film corresponding to the non-image areas are black, preventing the light hardening process, so the areas not struck by light can be removed during development. The light-hardened surfaces of a negative-working plate are therefore oleophilic and will accept ink while the non-image areas that have had the coating removed through the action of a developer are desensitized and are therefore hydrophilic.
Various useful printing plates that can be either negative-working or positive-working are described, for example, in GB 2,082,339 (Horsell Graphic Industries), and U.S. Pat. No. 4,927,741 (Garth et al), both of which describe imaging layers containing an o-diazonaphthoquinone and a resole resin, and optionally a novolac resin. Another plate that can be similarly used is described in U.S. Pat. No. 4,708,925 (Newman) wherein the imaging layer comprises a phenolic resin and a radiation-sensitive onium salt. This imaging composition can also be used for the preparation of a direct laser addressable printing plate, that is imaging without the use of a photographic transparency.
Direct digital imaging of offset printing plates is a technology that has assumed importance to the printing industry. The first commercially successful workings of such technology made use of visible light-emitting lasers, specifically argon-ion and frequency doubled Nd:YAG lasers. Printing plates with high photosensitivities are required to achieve acceptable through-put levels using plate-setters equipped with practical visible-light laser sources. Inferior shelf-life, loss in resolution and the inconvenience of handling materials under dim lighting are trade-offs that generally accompany imaging systems exhibiting sufficiently high photosensitivities.
Advances in solid-state laser technology have made high-powered diode lasers attractive light sources for plate-setters. Currently, at least two printing plate technologies have been introduced that can be imaged with laser diodes emitting in the infrared regions, specifically at about 830 nm. One of these is described in EP 573,091 (Agfa) and in several patents and published applications assigned to Presstek, Inc [for example, U.S. Pat. No. 5,353,705 (Lewis et al), U.S. Pat. No. 5,351,617 (Williams et al), U.S. Pat. No. 5,379,698 (Nowak et al), U.S. Pat. No. 5,385,092 (Lewis et al) and U.S. Pat. No. 5,339,737 (Lewis et al)]. This technology relies upon ablation to physically remove the imaging layer from the printing plate. Ablation requires high laser fluences, resulting in lower through-puts and problems with debris after imaging.
A higher speed and cleaner technology is described, for example, in U.S. Pat. No. 5,340,699 (Haley et al), U.S. Pat. No. 5,372,907 (Haley et al), U.S. Pat. No. 5,466,557 (Haley et al) and EP-A-0 672 954 (Eastman Kodak) which uses near-infrared energy to produce acids in an imagewise fashion. These acids catalyze crosslinking of the coating in a post-exposure heating step. Precise temperature control is required in the heating step. The imaging layers in the plates of U.S. Pat. No. 5,372,907 (noted above) comprise a resole resin, a novolac resin, a latent Bronsted acid and an infrared absorbing compound. Other additives, such as various photosensitizers, may also be included.
DE-4,426,820 (Fuji) describes printing plates that can be imaged in the near infrared at moderate power levels with relatively simple processing requirements. In one embodiment, the printing plate has at least two layers: an imaging layer containing an o-diazonaphthoquinone compound and an infrared absorbing compound, and a protective overcoat containing a water-soluble polymer or silicone polymer. Other plates have a single layer. In all cases, the plates are floodwise exposed with ultraviolet light to convert the o-diazonaphthoquinone to an indenecarboxylic acid, which is then imagewise decarboxylated by means of heat transferred from the infrared absorbing material. Development with an alkaline solution results in removal of areas not subjected to thermal decarboxylation. The pre-imaging floodwise exposure step, however, is awkward in that it precludes the direct loading of the printing plates into plate-setters.
Thus, there is a need for positive-working printing plates that can be easily imaged in the near infrared at moderate power levels and that can be directly processed after imaging.
SUMMARY OF THE INVENTION
The problems noted above with known photosensitive compositions and printing plates are overcome with a positive-working imaging composition consisting essentially of:
a) (i) a mixture of a phenolic resin and an o-diazonaphthoquinone derivative,
(ii) a reaction product of a phenolic resin and an o-diazonaphthoquinone reactive derivative, or
(iii) a mixture of (i) and (ii) and
b) a compound that absorbs infrared radiation at a maximum absorption wavelength greater than 750 nm,
wherein the weight ratio of b) to the diazonaphthoquinone of a) is less than 1:14.
This invention also provides an element consisting essentially of a support having thereon a positive-working imaging layer consisting essentially of the imaging composition described above.
This invention also provides a method of creating a positive image consisting essentially of the steps of:
A) providing an element as described above,
B) without prior or simultaneous floodwise exposure, imagewise exposing the element with an infrared radiation emitting laser, and
C) contacting the element with an aqueous developing solution to remove the image areas.
The imaging composition and element of this invention are useful for providing high quality positive images using moderately powered lasers. This makes the element much more convenient to use in plate-setters. The element of this invention also does not need a protective overcoat thereby eliminating the materials and coating step required for such layers. Moreover, such elements are imagewise exposed without any prior or simultaneous floodwise exposure to

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