......DE....FRGB................................................................
R
0800928
EUROPEAN PATENT APPLICATION
A1
19971015
EP
97200832.0
19970320
en
en
en
96200972
19960409
EP
19971015
199742
19971015
199742
6
6B 41M 5/36 A
6B 41C 1/10 B
de
Wärmeempfindliches Aufzeichnungselement und Verfahren zur Herstellung von Flachdruckplatten damit
en
A heat sensitive imaging element and a method for producing lithographic plates therewith
fr
Elément d'enregistrement thermosensible et procédé pour la fabrication de plaques lithographiques utilisant cet élément
AGFA-GEVAERT naamloze vennootschap
00200390
GV 96045
Septestraat 27
2640 Mortsel
BE
Van Damme, Marc
c/o Agfa-Gevaert N.V., IIE 3800, Septestraat 2
2640 Mortsel
BE
Vermeersch, Joan
c/o Agfa-Gevaert N.V., IIE 3800, Septestraat 2
2640 Mortsel
BE
DE
FR
GB
According to the present invention there is provided a heat sensitive imaging element comprising on a hydrophilic surface of a lithographic base an image forming layer comprising hydrophobic thermoplastic polymer particles dispersed in a water insoluble alkali soluble or swellable resin and a compound capable of converting light into heat, said compound being present in said image forming layer or a layer adjacent thereto, characterized in that said alkali swellable or soluble resin comprises phenolic hydroxy groups.

1. Field of the invention.
The present invention relates to a heat sensitive material for making a lithographic printing plate. The present invention further relates to a method for preparing a printing plate from said heat sensitive material.

2. Background of the invention.
Lithography is the process of printing from specially prepared surfaces, some areas of which are capable of accepting lithographic ink, whereas other areas, when moistened with water, will not accept the ink. The areas which accept ink form the printing image areas and the ink-rejecting areas form the background areas.
In the art of photolithography, a photographic material is made imagewise receptive to oily or greasy ink in the photo-exposed (negative working) or in the non-exposed areas (positive working) on a hydrophilic background.
In the production of common lithographic plates, also called surface litho plates or planographic printing plates, a support that has affinity to water or obtains such affinity by chemical treatment is coated with a thin layer of a photosensitive composition. Coatings for that purpose include light-sensitive polymer layers containing diazo compounds, dichromate-sensitized hydrophilic colloids and a large variety of synthetic photopolymers. Particularly diazo-sensitized systems are widely used.
Upon imagewise exposure of the light-sensitive layer the exposed image areas become insoluble and the unexposed areas remain soluble. The plate is then developed with a suitable liquid to remove the diazonium salt or diazo resin in the unexposed areas.
On the other hand, methods are known for making printing plates involving the use of imaging elements that are heat sensitive rather than photosensitive. A particular disadvantage of photosensitive imaging elements such as described above for making a printing plate is that they have to be shielded from the light. Furthermore they have a problem of sensitivity in view of the storage stability and they show a lower resolution. The trend towards heat sensitive printing plate precursors is clearly seen on the market.
For example, Research Disclosure no. 33303 of January 1992 discloses a heat sensitive imaging element comprising on a support a cross-linked hydrophilic layer containing thermoplastic polymer particles and an infrared absorbing pigment such as e.g. carbon black. By image-wise exposure to an infrared laser, the thermoplastic polymer particles are image-wise coagulated thereby rendering the surface of the imaging element at these areas ink acceptant without any further development. A disadvantage of this method is that the printing plate obtained is easily damaged since the non-printing areas may become ink accepting when some pressure is applied thereto. Moreover, under critical conditions, the lithographic performance of such a printing plate may be poor and accordingly such printing plate has little lithographic printing latitude.
EP-A-514145 discloses a heat sensitive imaging element including a coating comprising core-shell particles having a water insoluble heat softenable core component and a shell component which is soluble or swellable in aqueous alkaline medium. Red or infrared laser light directed image-wise at said imaging element causes selected particles to coalesce, at least partially, to form an image and the non-coalesced particles are then selectively removed by means of an aqueous alkaline developer. Afterwards a baking step is performed. However the printing endurance of a so obtained printing plate is low.
EP-A-599510 discloses a heat sensitive imaging element which comprises a substrate coated with (i) a layer which comprises (1) a disperse phase comprising a water-insoluble heat softenable component A and (2) a binder or continuous phase consisting of a component B which is soluble or swellable in aqueous, preferably aqueous alkaline medium, at least one of components A and B including a reactive group or precursor therefor, such that insolubilisation of the layer occurs at elevated temperature and/or on exposure to actinic radiation , and (ii) a substance capable of strongly absorbing radiation and transferring the energy thus obtained as heat to the disperse phase so that at least partial coalescence of the coating occurs. After image-wise irradiation of the imaging element and developing the image-wise irradiated plate, said plate is heated and/or subjected to actinic irradiation to effect insolubilisation. However the printing endurance of a so obtained printing plate is low.
EP-A-625728 discloses an imaging element comprising a layer which is sensitive to UV- and IR-irradiation and which can be positive or negative working. This layer comprises a resole resin,a novolac resin, a latent Bronsted acid and an IR-absorbing substance. The printing results of a lithographic plate obtained by irradiating and developing said imaging element are poor.
US-P-5,340,699 is almost identical with EP-A-625728 but discloses the method for obtaining a negative working IR-laser recording imaging element. The IR-sensitive layer comprises a resole resin,a novolac resin, a latent Bronsted acid and an IR-absorbing substance. The printing results of a lithographic plate obtained by irradiating and developing said imaging element are poor.
US-P-4,708,925 discloses a positive working imaging element including a photosensitive composition comprising an alkali-soluble novolac resin and an onium-salt. This composition can optionally contain an IR-sensitizer. After image-wise exposing said imaging element to UV - visible - or eventually IR-radiation followed by a development step with an aqueous alkali liquid there is obtained a positive working printing plate. The printing results of a lithographic plate obtained by irradiating and developing said imaging element are poor.
FR 1,561,957 discloses an imaging element comprising atleast a recording layer comprising a binder and a liquid or solid compound dispersed in said binder, the liquid or solid compound being more hydrophobic than the binder and forming at least partially a mixture compatible with said binder when heated. Said binders can be compounds which are insoluble in water or only partially soluble in wateri.e. binders which comprise only a limited number of solubilizing groups such as alcohols or acids. The printing results of a lithographic plate obtained by irradiating and developing said imaging element are poor.
All the disclosed systems either require a treatment after the development step and/or or yield lithographic plates with poor printing properties. So, there is still a need for a heat sensitive imaging element that is easy to process and yields a lithographic plate with good or excellent printing properties.

3. Summary of the invention.
It is an object of the present invention to provide a heat sensitive imaging element for making in a convenient way a lithographic printing plate having excellent printing properties.
It is another object of the present invention to provide a method for obtaining in a convenient way a negative working lithographic printing plate of a high quality using said imaging element.
Further objects of the present invention will become clear from the description hereinafter.
According to the present invention there is provided a heat sensitive imaging element comprising on a hydrophilic surface of a lithographic base an image forming layer comprising hydrophobic thermoplastic polymer particles dispersed in a water insoluble alkali soluble or swellable resin and a compound capable of converting light into heat, said compound being present in said image forming layer or a layer adjacent thereto, characterized in that said alkali swellable or soluble resin comprises phenolic hydroxy groups.
According to the present invention there is also provided a method for obtaining a lithographic printing plate comprising the steps of:
- (a) image-wise or information-wise exposing to light or heat an imaging element as described above
- (b) developing said exposed imaging element with an aqueous alkaline developing solution in order to remove the unexposed areas and thereby form a lithographic printing plate.

4. Detailed description of the invention.
It has been found that lithographic printing plates of high quality, especially with a high printing endurance can be obtained according to the method of the present invention using an imaging element as described above. More precisely it has been found that said printing plates are of high quality and are provided in a convenient way, thereby offering economical and ecological advantages.
In the context of the present application it is said that a compound is insoluble in a solvent when less than 0.1 g of said compound dissolves in said solvent at 20°C and it is said that a compound is soluble in a solvent when at least 1 g of said compound dissolves in said solvent at 20°C.
An imaging element for use in accordance with the present invention comprises on a hydrophilic surface of a lithographic base an image forming layer comprising hydrophobic thermoplastic polymer particles dispersed in a water insoluble alkali soluble or swellable resin having phenolic hydroxy groups as hydrophilic binder.
Preferred hydrophilic binders for use in an image forming layer in connection with this invention are for example synthetic novolac resins such as ALNOVOL, a registered trade mark of Reichold Hoechst and DUREZ, a registered trade mark of OxyChem and synthetic polyvinylfenols such as MARUKA LYNCUR M, a registered trade mark of Dyna Cyanamid.
The hydrophilic binder used in connection with the present invention is preferably not cross-linked or only slightly cross-linked.
According to one embodiment of the present invention, the lithographic base can be an anodised aluminum. A particularly preferred lithographic base is an electrochemically grained and anodised aluminum support. According to the present invention, an anodised aluminum support may be treated to improve the hydrophilic properties of its surface. For example, the aluminum support may be silicated by treating its surface with sodium silicate solution at elevated temperature, e.g. 95°C. Alternatively, a phosphate treatment may be applied which involves treating the aluminum oxide surface with a phosphate solution that may further contain an inorganic fluoride. Further, the aluminum oxide surface may be rinsed with a citric acid or citrate solution. This treatment may be carried out at room temperature or can be carried out at a slightly elevated temperature of about 30 to 50°C. A further interesting treatment involves rinsing the aluminum oxide surface with a bicarbonate solution. It is further evident that one or more of these post treatments may be carried out alone or in combination.
According to another embodiment in connection with the present invention, the lithographic base comprises a flexible support, such as e.g. paper or plastic film, provided with a cross-linked hydrophilic layer. A particularly suitable cross-linked hydrophilic layer may be obtained from a hydrophilic binder cross-linked with a cross-linking agent such as formaldehyde, glyoxal, polyisocyanate or a hydrolysed tetra-alkylorthosilicate. The latter is particularly preferred.
As hydrophilic binder there may be used hydrophilic (co)polymers such as for example, homopolymers and copolymers of vinyl alcohol, acrylamide, methylol acrylamide, methylol methacrylamide, acrylic acid, methacrylic acid, hydroxyethyl acrylate, hydroxyethyl methacrylate or maleic anhydride/vinylmethylether copolymers. The hydrophilicity of the (co)polymer or (co)polymer mixture used is preferably the same as or higher than the hydrophilicity of polyvinyl acetate hydrolyzed to at least an extent of 60 percent by weight, preferably 80 percent by weight.
The amount of crosslinking agent, in particular of tetraalkyl orthosilicate, is preferably at least 0.2 parts by weight per part by weight of hydrophilic binder, preferably between 0.5 and 5 parts by weight, more preferably between 1.0 parts by weight and 3 parts by weight.
A cross-linked hydrophilic layer in a lithographic base used in accordance with the present embodiment preferably also contains substances that increase the mechanical strength and the porosity of the layer. For this purpose colloidal silica may be used. The colloidal silica employed may be in the form of any commercially available water-dispersion of colloidal silica for example having an average particle size up to 40 nm, e.g. 20 nm. In addition inert particles of larger size than the colloidal silica can be added e.g. silica prepared according to Stöber as described in J. Colloid and Interface Sci., Vol. 26, 1968, pages 62 to 69 or alumina particles or particles having an average diameter of at least 100 nm which are particles of titanium dioxide or other heavy metal oxides. By incorporating these particles the surface of the cross-linked hydrophilic layer is given a uniform rough texture consisting of microscopic hills and valleys, which serve as storage places for water in background areas.
The thickness of a cross-linked hydrophilic layer in a lithographic base in accordance with this embodiment may vary in the range of 0.2 to 25 µm and is preferably 1 to 10 µm.
Particular examples of suitable cross-linked hydrophilic layers for use in accordance with the present invention are disclosed in EP-A 601240, GB-P-1419512, FR-P-2300354, US-P-3971660, US-P-4284705 and EP-A 514490.
As flexible support of a lithographic base in connection with the present embodiment it is particularly preferred to use a plastic film e.g. substrated polyethylene terephthalate film, cellulose acetate film, polystyrene film, polycarbonate film etc... The plastic film support may be opaque or transparent.
It is particularly preferred to use a polyester film support to which an adhesion improving layer has been provided. Particularly suitable adhesion improving layers for use in accordance with the present invention comprise a hydrophilic binder and colloidal silica as disclosed in EP-A 619524, EP-A 620502 and EP-A 619525. Preferably, the amount of silica in the adhesion improving layer is between 200 mg per m^2 and 750 mg per m^2. Further, the ratio of silica to hydrophilic binder is preferably more than 1 and the surface area of the colloidal silica is preferably at least 300 m^2 per gram, more preferably at least 500 m^2 per gram.
In accordance with the present invention, on top of a hydrophilic surface there is provided an image forming layer. Optionally, there may be provided one or more intermediate layers between the lithographic base and the image forming layer. An image forming layer in connection with the present invention comprises thermoplastic polymer particles dispersed in a water insoluble alkali soluble or swellable resin having phenolic hydroxy groups as hydrophilic binder.
Hydrophobic thermoplastic polymer particles used in connection with the present invention preferably have a coagulation temperature above 35°C and more preferably above 50°C. Coagulation may result from softening or melting of the thermoplastic polymer particles under the influence of heat. There is no specific upper limit to the coagulation temperature of the thermoplastic hydrophobic polymer particles, however the temperature should be sufficiently below the decomposition of the polymer particles. Preferably the coagulation temperature is at least 10°C below the temperature at which the decomposition of the polymer particles occurs. When said polymer particles are subjected to a temperature above coagulation temperature they coagulate to form a hydrophobic agglomerate in the hydrophilic layer so that at these parts the hydrophilic layer becomes insoluble in plain water or in an aqueous liquid.
Specific examples of hydrophobic polymer particles for use in connection with the present invention are e.g. polyethylene, polyvinyl chloride, polymethyl (meth)acrylate, polyethyl (meth)acrylate, polyvinylidene chloride, polyacrylonitrile, polyvinyl carbazole etc. or copolymers thereof. Most preferably used is polyethylene.
The weight average molecular weight of the polymers may range from 5,000 to 1,000,000g/mol.
The hydrophobic particles may have a particle size from 0.01 µm to 50 µm, more preferably between 0.05 µm and 10 µm and most preferably between 0.05 µm and 2 µm.
The polymer particles are present as a dispersion in the aqueous coating liquid of the image forming layer and may be prepared by the methods disclosed in US-P-3,476,937. Another method especially suitable for preparing an aqueous dispersion of the thermoplastic polymer particles comprises:
- dissolving the hydrophobic thermoplastic polymer in an organic water immiscible solvent,
- dispersing the thus obtained solution in water or in an aqueous medium and
- removing the organic solvent by evaporation.
The amount of hydrophobic thermoplastic polymer particles contained in the image forming layer is preferably between 20% by weight and 65% by weight and more preferably between 25% by weight and 55% by weight and most preferably between 30% by weight and 45% by weight.
The image forming layer can also comprise crosslinking agents although this is not necessary. Preferred crosslinking agents are low molecular weight substances comprising a methylol group such as for example melamine-formaldehyde resins, glycoluril-formaldehyde resins, thiourea-formaldehyde resins, guanamine-formaldehyde resins, benzoguanamine-formaldehyde resins. A number of said melamine-formaldehyde resins and glycoluril-formaldehyde resins are commercially available under the trade names of CYMEL (Dyno Cyanamid Co., Ltd.) and NIKALAC (Sanwa Chemical Co., Ltd.)
The imaging element further includes a compound capable of converting light to heat. This compound is preferably comprised in the image forming layer but can also be provided in a layer adjacent to the image forming layer. Suitable compounds capable of converting light into heat are preferably infrared absorbing components although the wavelength of absorption is not of particular importance as long as the absorption of the compound used is in the wavelength range of the light source used for image-wise exposure. Particularly useful compounds are for example dyes and in particular infrared dyes, carbon black, metal carbides, borides, nitrides, carbonitrides, bronze-structured oxides and oxides structurally related to the bronze family but lacking the A component e.g. WO_{2.9}. It is also possible to use conductive polymer dispersion such as polypyrrole or polyaniline-based conductive polymer dispersions. The lithographic performance and in particular the print endurance obtained depends on the heat-sensitivity of the imaging element. In this respect it has been found that carbon black yields very good and favorable results.
A light to heat converting compound in connection with the present invention is most preferably added to the image forming layer but at least part of the light to heat converting compound may also be comprised in a neighbouring layer. Such layer can be for example the cross-linked hydrophilic layer of the lithographic base according to the second embodiment of lithographic bases explained above.
In accordance with a method of the present invention for obtaining a printing plate, the imaging element is image-wise exposed and subsequently developed with an aqueous alkaline solution
Image-wise exposure in connection with the present invention is preferably an image-wise scanning exposure involving the use of a laser or L.E.D.. It is highly preferred in connection with the present invention to use a laser emitting in the infrared (IR) and/or near-infrared, i.e. emitting in the wavelength range 700-1500nm. Particularly preferred for use in connection with the present invention are laser diodes emitting in the near-infrared.
After the development of an image-wise exposed imaging element with an aqueous alkaline solution and drying the obtained plate can be used as a printing plate as such. However, it is still possible to bake said plate at a temperature between 100°C and 230°C for a period of 40 minutes to 5 minutes. For example the exposed and developed plates can be baked at a temperature of 230°C for 5 minutes, at a temperature of 150°C for 10 minutes or at a temperature of 120°C for 30 minutes.
The following example illustrates the present invention without limiting it thereto. All parts are by weight unless otherwise specified.

EXAMPLE 1

Preparation of the lithographic base
A 0.20 mm thick aluminum foil was degreased by immersing the foil in an aqueous solution containing 5 g/l of sodium hydroxide at 50°C and rinsed with demineralized water. The foil was then electrochemically grained using an alternating current in an aqueous solution containing 4 g/l of hydrochloric acid, 4 g/l of hydroboric acid and 5 g/l of aluminum ions at a temperature of 35°C and a current density of 1200 A/m^2 to form a surface topography with an average center-line roughness Ra of 0.5 µm.
After rinsing with demineralized water the aluminum foil was then etched with an aqueous solution containing 300 g/l of sulfuric acid at 60°C for 180 seconds and rinsed with demineralized water at 25°C for 30 seconds.
The foil was subsequently subjected to anodic oxidation in an aqueous solution containing 200 g/l of sulfuric acid at a temperature of 45°C, a voltage of about 10 V and a current density of 150 A/m^2 for about 300 seconds to form an anodic oxidation film of 3.00 g/m^2 of Al_2O_3, then washed with demineralized water, posttreated with a solution containing 20 g/l of sodium bicarbonate at 40°C for 30 seconds, subsequently rinsed with demineralized water at 20°C during 120 seconds and dried.
The grained and anodized lithographic base was then submersed in an aqueous solution containing 5 % w/w of citric acid for 60 seconds, rinsed with demineralized water and dried at 40°C.

Preparation of the imaging element
An imaging element according to the invention was produced by preparing the following coating composition and coating it to the above described lithographic base in an amount of 30 g/m^2 (wet coating amount) and drying it at 35°C.

Preparation of the coating composition
To 0.48 g of MARUKA LYNCUR M H-2 (a homopolymer of polyvinylphenol from Maruzen Co.) was added 14.32 g of a 1 % w/w NaOH solution in water. To 6.17 g of the above obtained solution was added 29.33 g water, 2.50 g of a 20 % w/w dispersion of polymethylmethacrylate (particle diameter of 90 nanometer) stabilized with the polyethyleneoxide surfactant Hostapal B (1% w/w vs. polymer) in deionized water, 2.00 g of a 15 % w/w dispersion of carbon black and 0.4 ml of a solution of a wetting agent in water.

Preparation of a printing plate and making copies of the original
An imaging element as described above was subjected to a scanning NdYLF infra red laser emitting at 1.05 µm (scanspeed 4 m/s and 8 m/s, spot size 15 µm and the power on the plate surface was varied from 120 to 540 mW ).
After imaging the plate was processed with Fuji PS-plate developer DP-5 (an alkaline aqueous developer) to remove the unexposed areas resulting in a negative working lithographic printing plate.
The obtained lithographic printing plate could be used to print on a conventional offset press using a commonly employed ink and fountain. Excellent copies and a high printing endurance were obtained.
1. A heat sensitive imaging element comprising on a hydrophilic surface of a lithographic base an image forming layer comprising hydrophobic thermoplastic polymer particles dispersed in awater insoluble alkali soluble or swellable resin and a compound capable of converting light into heat, said compound being present in said image forming layer or a layer adjacent thereto, characterized in that said alkali swellable or soluble resin comprises phenolic hydroxy groups.
2. A heat sensitive imaging element according to claim 1 wherein said water insoluble alkali swellable or soluble resin comprising phenolic hydroxy groups is a novolac resin or a polyvinylphenol resin.
3. A heat sensitive imaging element according to claim 1 or 2 wherein said thermoplastic polymer particles have a coagulation temperature of at least 35°C.
4. A heat sensitive imaging element according to any of claims 1 to 3 wherein said thermoplastic polymer particles are selected from the group consisting of polyethylene, polystyrene, polymethyl(meth)acrylate, polyethyl(meth)acrylate, polyvinylchloride, polyvinylidenechloride, polyacrylonitrile and polyvinylcarbazole and copolymers thereof.
5. A heat sensitive imaging element according to any of claims 1 to 4 wherein said compound capable of converting light into heat is selected from the group consisting of an infrared absorbing dye, carbon black, a metal boride, a metal carbide, a metal nitride, a metal carbonitride and a conductive polymer dispersion.
6. A heat sensitive imaging element according to any of claims 1 to 5 wherein said lithographic base is anodized aluminum or comprises a flexible support having thereon a cross-linked hydrophilic layer.
7. A heat sensitive imaging element according to any of claims 1 to 6 wherein said image forming layer comprises a cross-linking agent.
8. A heat sensitive imaging element according to any of claims 1 to 7 wherein said compound capable of converting light to heat is present in said image forming layer.
9. A method for obtaining a lithographic printing plate comprising the steps of:
(a) image-wise or information-wise exposing to light or heat an imaging element according to any of claims 1 to 8,
(b) developing said exposed imaging element with an aqueous alkaline developing solution in order to remove the unexposed areas and thereby form a lithographic printing plate.
10. A method for obtaining a lithographic plate according to claim 9 wherein said exposed and developed imaging element is baked at a temperature between 100°C and 230°C for a period of 40 minutes to 5 minutes.