JP2002321332A - On-press coating and on-press process of planographic material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an on-press coating, on-press exposure, and on-press processing method applicable to all the planographic printing machines including a printing machine excluding the supply of dampening water and make the suspending hours of the printing machine the shortest. SOLUTION: A planography method consists of seven stages: (i) a web of flexible planographic base having a hydrophilic surface is wound off a supply spool, (ii) the planographic base is wound around a plate cylinder of the printing machine, (iii) an image recording layer removable in a single-fluid ink or removable by being exposed to heat or light is applied on the planographic base, (iv) the image recording layer is exposed to the heat or the light as it is, (v) the image recording layer is processed by supplying the single-fluid ink whereby a printing master is obtained, (vi) printing is conducted by supplying the single- fluid ink to the printing master installed on the plate cylinder of the printing machine, and (vii) the printing master is removed from the plate cylinder, preferably taken up, by winding up on the spool.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to a process for unwinding a lithographic base from a supply roll, wrapping it around the cylinder of a printing machine, and on-press coating with an image-recording layer, which is then image-wise. Exposed and single-fluid ink (single-
lithographic printing method which processes by supplying fluid ink).

[0002]

2. Description of the Related Art A lithographic printing press uses a so-called printing master, such as a printing plate, which is placed on the cylinder of the printing press. The master carries the lithographic image on its surface and supplies ink over the image and then prints are obtained by transferring the ink from the master to a receiver material, typically paper. In conventional lithographic printing, ink and fountain solution (also referred to as fountain solution) contain lipophilic (or hydrophobic, ie, ink-receptive, water-repellent) regions and hydrophilic (or oleophobic, ie, water- (Receptive, ink-repellent) areas. In so-called driographic printing, the lithographic image consists of ink-receptive and ink-adhesive (ink-repellent) areas, and during driographic printing only ink is supplied to the master.

[0003] Print masters are generally obtained by the so-called computer-to-film method, in which, for example, typeface selection, scanning,
Various print preparation steps such as color separation, screening, trapping, layout and imposition are performed digitally and each color selection is transferred to a print film using an image-setter. After processing, the film can be used as a mask for exposing the imaging material, referred to as a plate precursor, and after plate processing, a printing plate is obtained that can be used as a master.

In the last few years, much interest has been drawn to the so-called computer-to-plate method. Direct-to-plate (direc
This method, also referred to as the t-to-plate method, avoids the creation of films because the digital document is transferred directly to the plate precursor by a so-called plate-setter. A particular type of CTP method involves exposing the plate precursor while being placed on the plate cylinder of the printing press by an image-setter integrated into the printing press. This method is sometimes referred to as "computer-to-press" and printing machines with an integrated image-setter are sometimes referred to as digital printing machines. Review of Digital Printing Machines from Proceedings of the Imaging Sc
ience &Technology's 1997 International Conference
on Digital Printing Technologies (Non-Impact Prin
ting 13). Computer-to-press methods are described, for example, in EP-A 770 495, EP-A
A 770 496, WO 94001280, EP-A
580 394 and EP-A 774 364. EP-A 640 478 describes a digital printing machine with an automatic plate-filling system comprising a supply roll and a take-up roll in a plate cylinder.

[0005] Typical plate materials used in computer-to-press processes are based on ablation. A problem with ablated plates is the generation of debris that is difficult to remove and may interfere with the printing process or contaminate the exposed optics of the integrated image-setter. Another way is
It requires wet processing with chemicals that may damage or contaminate the electronics and optics of the integrated image-setter and other equipment of the printing machine.
Therefore, lithographic coatings that do not require a wet treatment or that can be treated with fresh water, ink or fountain solution are particularly desirable in a computer-to-press process. WO 9
0002044, WO 91008108 and EP-
A 580 394 discloses such plates, but they are all ablated plates with a multilayer structure which is less suitable for on-press coating. US 6,095,04
8 is a single-ablation-type material using a fluid ink (abl
ation-type material).

[0006] A non-ablative plate which can be treated with fountain solution and ink is described in EP-B 770 494. The latter patent specification discloses an image-wise exposure of an image-forming material comprising an image-recording layer of a hydrophilic binder, a compound capable of converting light to heat, and hydrophobic thermoplastic polymer particles. The exposed areas are converted to a hydrophobic phase that defines the print areas of the print master. Since the layers are treated by the interaction of the fountain solution and the ink supplied to the cylinder during the operation of the printing press, the operation of the printing press can be started immediately after exposure without further processing. As such, the wet chemical treatment of these materials is "hidden" to the user and occurs during the first few runs of the printing press.

[0007] A problem with the latter method is that the on-fountain solution is supplied first and then the ink is supplied to the plate.
Pressing is performed, which can be easily performed in a printing machine in which the ink and the fountain roller can be engaged independently of each other. However, it is more difficult to optimize the on-press process by the simultaneous application of fountain solution and ink, which is a choice only in printing machines equipped with an integrated ink / fountain solution supply.

[0008] Furthermore, the treatment of the plate material with a fountain solution is not possible in driographic printing machines, because in such printing machines only ink is supplied to the plate. Driographic printing machines require careful temperature control because there is no cooling effect from the aqueous dampening solution.

Therefore, there is a need for a method for performing on-press processing of an imaging material without the supply of an aqueous dampening solution.

[0010] The plate precursor usually comprises a sheet-like support and one or more functional coatings, but is coated with a composition capable of forming a lithographic surface with image-wise exposure and optional processing. A computer-to-press method applied directly on the surface of a plate cylinder of a machine was described, for example, in GB 1465532. E
PA 101 266 describes the coating of a hydrophobic layer directly on the hydrophilic surface of a plate cylinder. After removal of the non-printed areas by ablation, a master is obtained. However, as discussed above, ablation should be avoided in a computer-to-press method. US-P
5,713,287 are so-called switchable, such as, for example, tetrahydro-pyranyl methyl methacrylate.
tchable) describes a computer-to-press method in which a polymer is applied directly onto the surface of a plate cylinder. The switchable polymer is converted from initial water-sensitive to water-insensitive by image-wise exposure.

A problem with known on-press coating methods is that after printing, the coating is removed from the plate cylinder so that the next cycle of on-press coating, exposure, processing and printing can begin. During the time required for this cleaning step, the printing machine does not produce printing. The downtime of the printing machine should be minimized.

[0012]

SUMMARY OF THE INVENTION It is an object of the present invention to provide on-press coating, on-press coating applicable to all lithographic printing machines, including printing machines that do not include a fountain solution supply.
Press exposure, and to provide an on-press processing method. Another object is to minimize downtime of the printing machine. These objects are achieved by the method of claim 1.

[0013]

SUMMARY OF THE INVENTION On-press processing of an imaging element comprising an image-recording layer that is soluble in a single-fluid ink or that can be rendered soluble in a single-fluid ink by an exposure step. It has been found that excellent results are obtained by using a single-fluid ink for this purpose. Single-fluid inks are generally understood to be emulsions in the polar phase of the ink phase, or, conversely, emulsions in the polar phase of the ink phase. Single-fluid inks allow printing using conventional wet lithographic printing masters without the application of fountain solution. The ink phase adsorbs on the hydrophobic areas of the print master and the polar phase wets the hydrophilic areas, thereby preventing the adsorption of the ink components on the non-printed parts of the lithographic image.

The lithographic coating is not applied on the plate cylinder itself, but rather on a flexible lithographic base that is automatically supplied from the spool and then wound around the cylinder of the printing press. After the on-press coating, on-press exposure, on-press processing and printing, no cleaning steps are performed to remove the coating from the base. Instead, the print master is removed from the plate cylinder, and a new lithographic base is filled on the cylinder and turned on.
The next cycle of press coating, on-press exposure, on-press processing and printing can be started. This cycle can be repeated several times, the exact number of times depending on the length of the lithographic base web present on the supply spool. Preferably, the number of print cycles is more than 1, more preferably more than 10, and most preferably more than 30. Since the plate change and filling are completely automatic, downtime of the printing machine between printing cycles is minimized.

[0015] Further objects of the present invention will become clear from the detailed description. Specific features for preferred embodiments of the invention are set out in the dependent claims.

The imaging element used in the present invention comprises a flexible lithographic base and an image-recording layer. Lithographic Base The lithographic base comprises a web-form support that is sufficiently flexible to be wound on a spool. The support has a hydrophilic surface or is provided with a hydrophilic layer. The flexible support can consist of paper, plastic, thin metal, for example aluminum or a composite or laminate thereof, for example a laminate of plastic and metal. A very preferred example is a PET film laminated to aluminum that is thin enough to allow winding on a spool. Preferred examples of the plastic film include a polyethylene terephthalate (PET) film, a polynaphthalene ethylene film, a cellulose acetate film, a polystyrene film, and a polycarbonate film. The plastic film support may be opaque or transparent.

A particularly preferred lithographic base having a hydrophilic surface is an electrochemically polished and anodized aluminum support. The anodized aluminum support can be treated to improve the hydrophilic properties of its surface. For example, an aluminum support may be silicided by treating its surface with a sodium silicate solution at an elevated temperature, eg, 95 ° C. Or,
Phosphating may be applied, which involves treating the aluminum oxide surface with a phosphate solution that may further contain inorganic fluoride. Further, the aluminum surface may be rinsed with a citric acid or citrate solution. This treatment may be performed at room temperature or at a slightly elevated temperature of about 30-50 ° C. Another interesting treatment involves rinsing the aluminum oxide surface with a bicarbonate solution. In addition, the aluminum oxide surface is produced by reaction with polyvinylphosphonic acid, polyvinylmethylphosphonic acid, phosphate esters of polyvinyl alcohol, polyvinylsulfonic acid, polyvinylbenzenesulfonic acid, sulfate esters of polyvinyl alcohol, and sulfonated aliphatic aldehydes. May be treated with acetal of polyvinyl alcohol to be used. It is also clear that one or more of these post-treatments can be performed alone or in combination. A more detailed description of these processes is given in GB-A-1 084 070, DE-A-44.
23 140, DE-A-4 417907, EP-A
-659 909, EP-A- 537 633, DE-
A-4001 466, EP-A-292801, E
PA-291 760 and US-P-4 458
005.

A support having no hydrophilic surface can be provided with a hydrophilic layer called a base layer. The base layer is preferably a crosslinked hydrophilic layer obtained from a hydrophilic binder crosslinked with a hardener such as, for example, formaldehyde, glyoxal, polyisocyanate or hydrolyzed tetra-alkyl orthoformate. .
The latter is particularly preferred. The thickness of the hydrophilic base layer is 0.2 to
It can vary within the range of 25 μm and is preferably between 1 and 10 μm.

Hydrophilic binders for use in the base layer include, for example, hydrophilic (co) polymers such as vinyl alcohol, acrylamide, methylolacrylamide, methylolmethacrylamide, acrylic acid, methacrylic acid, hydroxyacrylate. Ethyl, hydroxyethyl methacrylate homopolymers and copolymers, or maleic anhydride / vinyl methyl ether copolymer. The hydrophilicity of the (co) polymer or (co) polymer mixture used is preferably at least 60% by weight, preferably 80% by weight.
% By weight, the same as or higher than the hydrophilicity of the hydrolyzed polyvinyl acetate.

The amount of hardener, especially tetraalkyl orthoformate, is preferably at least 0.2 parts by weight, more preferably between 0.5 and 5 parts by weight per part by weight of hydrophilic binder.
Most preferably between 1 and 3 parts by weight.

[0021] The hydrophilic base layer can contain substances that increase the mechanical strength and porosity of the layer. Colloidal silica can be used for this purpose. The colloidal silica used is, for example, 40 nm
Up to, for example, a commercially available aqueous dispersion of colloidal silica having an average particle size of 20 nm. In addition, inert particles larger in size than colloidal silica, such as J. Colloid and Interface Sci., Vol. 26, 1968,
Stover (S) as described on pages 62 to 69
Particles having an average diameter of at least 100 nm, which may be silica or alumina particles produced according to the toeber method, or particles of titanium dioxide or other heavy metal oxides. By introducing these particles,
The surface of the hydrophilic base layer is provided with a uniform rough texture consisting of fine irregularities, which serve as storage for water in the background area.

Particular examples of hydrophilic base layers suitable for use according to the invention are EP-A-601240, GB-P-
1 419 512, FR-P-2 300 354, U
SP-3 971 660 and US-P-428
No. 4,705.

It is particularly preferred to use a film support provided with an adhesion improving layer, also called an undercoat layer. Particularly suitable adhesion improving layers for use according to the invention are EP-A
-619 524, EP-A-620 502 and E
It comprises a hydrophilic binder and colloidal silica as disclosed in P-A-619 525. Preferably, the amount of silica in the adhesion improving layer is between 200 mg / m ² and
Between 750 mg / m ² . Furthermore, the ratio of silica to hydrophilic binder is preferably greater than 1 and the surface area of the colloidal silica is preferably at least 300 m ² /
Grams, more preferably at least 500 m ² / gram. Image-recording layer The image-forming material comprises at least one image-recording layer provided on a lithographic base. Preferably, only one layer is applied on the base. The material may be light- or heat-sensitive, the latter being preferred for sun-stability reasons.
The image-recording layer of the material used in the invention is preferably non-
It is ablative. The term "non-ablative"
Is understood to mean that the image-recording layer is not substantially removed during the exposure step. The material can be positive-acting, i.e. the exposed areas of the image-recording layer are made removable with a single-fluid ink, whereby the lithographic base hydrophilicity which defines the non-printing areas of the master Areas that expose the surface but are not exposed are not removable with the single-fluid ink and define the hydrophobic print area of the master. In a more preferred embodiment, the material is negative-working, that is, the unexposed areas of the image-recording layer are removable with a single-fluid ink, thereby defining a lithographic base-based non-printing area of the master. Although exposing the hydrophilic surface, the exposed areas are not removable with the single-fluid ink and define the hydrophobic printed areas of the master. The term removable means that the image-recording layer is made by supplying a single-fluid ink, for example by dissolving the layer in a single-fluid ink or by making a dispersion or emulsion of the layer in a single-fluid ink. Indicates that it can be removed from the lithographic base.

In a preferred embodiment, the imaging element comprises an image-recording layer that is negative-acting and is removable with a single-fluid ink before exposure and is made less removable upon exposure. Such negative working image-recording layer 2
Two very preferred embodiments are discussed below.

In a first very preferred embodiment, the mechanism of action of the imaging layer is, for example, EP 770494, EP 770
495, EP 770 497, EP 773 112,
As described in EP 774 364, and EP 849 090, preferably by heat-induced aggregation of hydrophobic thermoplastic polymer particles dispersed in a hydrophilic binder. The agglomerated polymer particles define hydrophobic print areas that are not easily removable with the single-fluid ink, while the unexposed layers are non-removable, non-removable with the single-fluid ink.
Specify the print area. Thermal condensation can be triggered, for example, by direct exposure to heat by a thermal head or by light absorption of one or more compounds that can convert light, more preferably infrared light, to heat. it can.
Particularly useful photo-thermal conversion compounds are, for example, dyes, pigments, carbon black, metal carbides, borides, nitrides, carbonitrides, bronze-structured oxides, and conductive polymer dispersions.
For example, conductive polymer dispersions based on polypyrrole, polyaniline or polythiophene. Infrared dyes and carbon black are highly preferred.

The hydrophobic thermoplastic polymer particles preferably have a particle size of 3
It has a solidification temperature above 5 ° C, and more preferably above 50 ° C. Coagulation occurs by softening or melting of the thermoplastic polymer particles under the influence of heat. There is no specific upper limit for the solidification temperature of the thermoplastic hydrophobic polymer particles, but the temperature must be sufficiently lower than the decomposition of the polymer particles. Preferably, the coagulation temperature is at least 10 ° C. below the temperature at which decomposition of the polymer particles occurs. Specific examples of the hydrophobic polymer particles include, for example, polyethylene, polyvinyl chloride, polymethyl (meth) acrylate, poly (ethyl methacrylate), polyvinylidene chloride, polyacrylonitrile, polyvinyl carbazole, polystyrene, and copolymers thereof. It is a polymer. Polystyrene is most preferably used.
The weight average molecular weight of the polymer is 5,000 to 1,000,000
It can be in the range of 0 g / mol. 0.01μ hydrophobic particles
m to 50 μm, more preferably 0.05 μm to 10 μm
And most preferably between 0.05 μm and 2 μm. The amount of hydrophobic thermoplastic polymer particles contained in the imaging layer is preferably 20
Wt% to 65 wt%, and more preferably between 25 wt% to 55 wt%, and most preferably between 30 wt% to 45 wt%.

Suitable hydrophilic binders are, for example, synthetic homo- or copolymers such as polyvinyl alcohol, poly (meth) acrylic acid, poly (meth) acrylamide, hydroxyethyl poly (meth) acrylate, polyvinyl methyl ether, or natural Binders such as gelatin, polysaccharides such as dextran, pullulan, cellulose, acacia, alginic acid.

In a second, highly preferred embodiment, the imaging layer is hydrophilic and soluble in the single-fluid ink before exposure and becomes hydrophobic and less soluble after such exposure. It comprises an aryldiazosulfonate homo- or copolymer. Exposure can be performed by the same means as discussed above with respect to thermal coagulation of the polymer particles. Alternatively, the aryldiazosulfonate polymer can be switched by exposure to ultraviolet light, for example, by an ultraviolet laser or an ultraviolet lamp.

Preferred examples of such an aryldiazosulfonate polymer include an aryldiazosulfonate monomer and another aryldiazosulfonate monomer and / or a vinyl monomer such as (meth) acrylic acid or an ester thereof. , (Meth) acrylamide, acrylonitrile, vinyl acetate, vinyl chloride, vinylidene chloride,
It is a compound that can be produced by homo- or copolymerization with styrene, α-methylstyrene and the like. Aryldiazosulfonate polymers suitable for use in the present invention have the formula:

[0030]

Embedded image

Wherein R ⁰ , ¹ and ² each independently represent hydrogen, an alkyl group, a nitrile or a halogen such as Cl, L represents a divalent linking group, n represents 0 or 1,
A represents an aryl group and M represents a cation. L is preferably ^{_{-X t -CONR 3 -, - X}} t -
COO -, - represents a divalent bonding group selected from the X- and -X _t -CO- the group consisting, wherein t is 0 or 1
The stands, R ³ represents hydrogen, an alkyl group or an aryl group, X represents an alkylene group, an arylene group, an alkylene group, arylene group, alkylenethio group, Arirenchio group, alkylene group, arylene group, oxygen, Represents a sulfur or amino group. A is preferably an unsubstituted aryl group, such as an unsubstituted phenyl group, or an aryl group substituted with one or more alkyl, aryl, alkoxy, aryloxy or amino groups, such as phenyl. Represent. M preferably represents a cation, for example NH ₄ ⁺ , or a metal ion such as Al, Cu, Zn, an alkaline earth metal or an alkali metal cation.

Aryldiazosulfonate monomers suitable for preparing the above polymers are EP-A 33939.
3, EP-A 507008 and EP-A 77164
5 is disclosed. Specific examples are:

[0033]

Embedded image

[0034]

Embedded image

[0035]

Embedded image

[0036]

Embedded image

The image-forming material can comprise further layers besides the image-recording layer. Such a separate layer is preferably applied on a lithographic base stored on a supply spool, so that only the image-recording layer is coated on-press. A preferred example is a light absorbing layer containing a light absorbing compound, such as a compound that converts light to heat.
An image-recording layer comprising, for example, hydrophobic thermoplastic polymer particles or an aryldiazosulfonate polymer as described above is applied on top of the light absorbing layer during the on-press coating step. Single-fluid inks Single-fluid inks suitable for use in the method of the present invention are described in US 4,045,232, US 4,981,517 and US 6,140,392. Single-fluid inks are generally emulsions in the polar phase of the ink phase or
Conversely, it is understood as an emulsion in the polar ink phase. The ink phase is also called the hydrophobic or lipophilic phase. The polar phase preferably comprises at least 50%, more preferably at least 70% and even more preferably at least 90% of the non-aqueous polar liquid. In a most preferred embodiment, the polar phase comprises an organic polar liquid and is essentially free of water. The polar liquid is preferably a polyol. A highly preferred single-fluid ink is WO 00/3
2705, and its related content is reproduced below.

[0038] The hydrophobic phase preferably comprises a vinyl resin having carboxyl functionality. The term "vinyl resin"
Include polymers produced by using a vinyl monomer and a monomer copolymerizable with the vinyl monomer through a carbon-carbon double bond by chain reaction polymerization or addition polymerization.
Representative vinyl monomers include, but are not limited to, vinyl esters, acrylic and methacrylic monomers, and vinyl aromatic monomers including styrene. The vinyl polymer may be branched by including a monomer having two reactive sites in the polymerization reaction.
If the vinyl polymer is branched, it nevertheless remains effectively soluble. "Soluble"
Means that the polymer can be diluted with one or more solvents. (In contrast, the polymer may be cross-linked into an insoluble three-dimensional network that is swollen only by the solvent.) The branched vinyl resin may have a sufficient degree of branching despite the degree of branching. Retains dilutability.

The carboxy-functional vinyl polymer includes at least one acid-functional monomer or at least one monomer having a group that is converted to an acid group after polymerization, such as an anhydride group. Can be produced by polymerization of a monomer mixture. Examples of acid-functional or anhydride-functional monomers are α, β-ethylenically unsaturated monocarboxylic acids having 3 to 5 carbon atoms, such as acrylic acid, methacrylic acid, and crotonic acid; Α, β-ethylenically unsaturated dicarboxylic acids, and anhydrides and monoesters of these acids, such as maleic anhydride and fumaric acid; and acid-functional derivatives of copolymerizable monomers, such as amber Includes, but is not limited to, hydroxyethyl acrylate half ester of an acid.

Includes acid-functional monomers that are hydrated to form acid groups after polymerization, such as acrylic acid, methacrylic acid, or crotonic acid, or anhydride monomers, such as maleic anhydride or itaconic acid. Is preferred.
The acid-functional vinyl polymer has an acid number of at least about 3 mg KOH per gram non-volatiles, preferably about 6 to about per gram non-volatiles, based on the non-volatile weight of the vinyl polymer. An acid number of 30 mg KOH, and more preferably about 8 to about 25 mg per gram of non-volatiles
It is preferable to have an acid value of KOH.

In a preferred embodiment, the acid-functional polymer is fully branched. The inks used in the present invention are preferably branched but effectively soluble vinyl polymers. The branched vinyl polymer may be diluted rather than swelled by the addition of a solvent. Branching can be performed by at least two methods.
In the first method, a monomer having two or more polymerizable double bonds is included in the polymerization reaction. In the second method, a pair of ethylenically unsaturated monomers is included in the monomer mixture to be polymerized, each of which is in addition to a polymerizable functional double bond on the other monomer. It has at least one additional functional group that is reactive with another functional group. Preferably, the reaction of the additional functional group occurs during the polymerization reaction,
This is not considered important and the reaction of the additional functional groups can be carried out partially or completely before or after the polymerization. Such pairs of various mutually reactive groups are possible. Illustrative examples of such pairs of reactive groups are epoxide and carboxyl, amine and carboxyl, epoxide and amine, amine and carboxyl, epoxide and amine, epoxide and anhydride, amine and anhydride Groups, hydroxyl and carboxyl or anhydride groups, amine and acid chloride groups, alkylene-imine and carboxyl groups, organoalkoxysilanes and carboxyl groups,
Includes, but is not limited to, isocyanate and hydroxyl groups, cyclic carbonate and amine groups, isocyanate and amine groups, and the like. If carboxyl or anhydride groups are included as one of the reactive groups, they are used in a sufficient excess in the vinyl resin to provide the required carboxyl functionality.
Specific examples of such monomers include glycidyl (meth) acrylate and (meth) acrylic acid, N-alkoxymethylated acrylamides, which react with itself, such as N-isobutoxy. It includes, but is not limited to, methylated acrylamide, gamma-methacryloxy trialkoxysilane (which reacts with itself), and combinations thereof.

Preferably, the vinyl resin has at least one singly unsaturated bond having two or more polymerizable ethylenically unsaturated bonds, and particularly preferably from 2 to about 4 polymerizable ethylenically unsaturated bonds. It is polymerized using a monomer. Illustrative examples of monomers having two or more ethylenically unsaturated moieties are the (meth) polyols, alone or in combination of two or more.
Acrylic esters such as 1,4-butanediol di (meth) acrylate and 1,6-di (meth) acrylic acid
Hexanediol, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylol methane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentapenta (meth) acrylate Erythritol, dipentaerythritol hexa (meth) acrylate, alkylene glycol di (meth) acrylate and polyalkylene glycols di (meth) acrylate, for example, polyethylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate Diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and polyethylene glycol di (meth) acrylate; divinylbenzene, allyl methacrylate, diphthalic acid Lil, encompasses and diallyl terephthalate, but are not limited to. Of these, divinylbenzene, butylene glycol dimethacrylate, butanediol dimethacrylate, trimethylolpropane triacrylate, and pentaerythritol tetra-acrylate are highly preferred, and divinylbenzene is even more highly preferred.

Preferably, the branched vinyl polymer is 10
At least about 0.0 per 0 gram of monomer to be polymerized
In addition to 08 equivalents of at least one monomer having at least two ethylenically unsaturated polymerizable bonds, or 0.0004 equivalents of ethylenically unsaturated polymerizable bonds per 100 grams of monomer to be polymerized. It is polymerized using each of two monomers having groups that are reactive with each other. Preferably, the branched vinyl polymer has at least about 0.012 to about 0.08 equivalents, and more preferably about 0.016 to about 0.064 equivalents, per 100 grams of monomer to be polymerized. A polyfunctional monomer or monomers having at least two ethylenically unsaturated polymerizable bonds or
It is polymerized using a pair of a monomer having one polymerized bond and a monomer having one additional mutually reactive group.

The polyfunctional monomer or monomers preferably have 2 to 4 ethylenically unsaturated polymerizable bonds, and more preferably have 2 ethylenically unsaturated polymerizable bonds. In one embodiment, from about 0.5% to about 6%, more preferably from about 1.2% to about 6%, even more preferably from about 1.2% to about 6%, based on the total weight of the monomers to be polymerized.
About 4%, and even more preferably from about 1.5% to
It is preferred to polymerize the branched vinyl resin by polymerizing a mixture of monomers containing about 3.25% divinylbenzene. (Technical divinylbenzene includes monofunctional and / or non-functional materials. The amount of technical material required to give the indicated percentage should be calculated. For example, 80% by weight of divinyl benzene/
5% by weight of the material, which is a 20% monofunctional monomer, will give 4% by weight of the divinylbenzene fraction. (1) divinylbenzene or another monomer having at least two polymerizable ethylenically unsaturated bonds, or (2) a monomer having a polymerizable group and additional monomers contained in the polymerization mixture. The optimal amount of reactive group pairs depends on the specific reaction conditions, such as the rate of addition of the monomers during polymerization, the solvency of the polymer formed in the selected reaction medium, It depends in part on the amount, the half-life of the initiator selected at the reaction temperature and the amount of initiator relative to the weight of the monomers, and can be determined by simple tests.

Another monomer that can be polymerized with a polyfunctional monomer and an acid-functional monomer (or a monomer having a group that can be subsequently converted to an acid group) is a C3-5 monomer. α, β−
Esters of ethylenically unsaturated monocarboxylic acids, for example, esters of acrylic acid, methacrylic acid, and crotonic acid; α, β-ethylenically unsaturated dicarboxylic acids having 4 to 6 carbon atoms, and anhydrides and monoacids of these acids. Esters and diesters, including but not limited to vinyl esters, vinyl ethers, vinyl ketones, and aromatic or heteroaliphatic vinyl compounds. Representative examples of suitable esters of acrylic acid, methacrylic acid, and crotonic acid are esters from reaction with saturated aliphatic and cycloaliphatic alcohols having 1 to 20 carbon atoms, such as acrylic acid, methacrylic acid, and Includes methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, 2-ethylhexyl, lauryl, stearyl, cyclohexyl, trimethylcyclohexyl, tetrahydrofurfuryl, stearyl, sulfoethyl, and isobornyl esters of crotonic acid However, it is not limited to them. Representative examples of other ethylenically unsaturated polymerizable monomers include anhydrides of fumaric, maleic, and itaconic acids, such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, and tert-butanol. Includes compounds such as, but not limited to, monoesters and diesters with alcohols. Representative examples of vinyl monomers for polymerization include, but are not limited to, compounds such as vinyl acetate, vinyl propionate, vinyl ethers such as vinyl ethyl ether, vinyl and vinylidene halides, and vinylidene ethyl ketone. is not. Representative examples of aromatic or heterocyclic aliphatic vinyl compounds include styrene, α-methylstyrene, vinyltoluene, tert.
Compounds such as, but not limited to, -butylstyrene and 2-vinylpyrrolidone. The choice of monomer is based on various factors normally considered in the manufacture of ink varnishes, including the desired glass transition temperature and the desired degree of dilution of the polymer formed in the solvent or solvent system of the ink composition.

Preferred vinyl polymers can be prepared by using free radical polymerization in the prior art, preferably in a semi-batch process. For example, the monomer, one or more initiators, and any chain transfer agent can be fed at a controlled rate into a suitably heated reactor filled with a solvent in a semi-batch process. it can. Typical sources of free radicals are organic peroxides, such as dialkyl peroxides such as di-tert-butyl peroxide and dicumyl peroxide, peroxyesters such as tert-butylperoxy 2-ethylhexanoate and tert-butylperoxy. Pivalates; peroxycarbonates and peroxydicarbonates, such as tert-butylperoxyisopropyl carbonate, di-2-ethylhexylperoxydicarbonate and dicyclohexylperoxydicarbonate; diacyl peroxides, such as dibenzoyl peroxide and dilauroyl peroxide;
Hydroperoxides such as cumene hydroperoxide and tert-butyl hydroperoxide; ketone peroxides such as cyclohexanone peroxide and methyl isobutyl ketone peroxide; and peroxyketals such as 1,1-bis (tert-butylperoxy) -3,5, 5-trimethylcyclohexane and 1,1-bis (tert-butylperoxy) cyclohexane; and azo compounds such as 2,2'-azobis (2-methylbutanenitrile), 2,2'-azobis (2-methyl) propio Nitriles and 1,1'-azobis (cyclohexanecarbonitrile). Organic peroxides are preferred. Tert-butyl peroxyisopropyl carbonate is particularly preferred. Chain transfer agents can be used during the polymerization. Representative chain transfer agents are mercaptans, such as octyl mercaptan, n
Or tert-dodecylmercaptan, thiosalicylic acid, mercaptocarboxylic acids such as mercaptoacetic acid and mercaptopropionic acid and their esters, and mercaptoethanol; halogenated compounds; and dimeric α-methylstyrene.
Preferably, no chain transfer agent is included due to odor and other known disadvantages. The particular initiator and amount of initiator used will depend on factors known to those skilled in the art, such as reaction temperature,
It depends on the amount and type of solvent (for solution polymerization), the half-life of the initiator and the like.

The addition polymerization is generally carried out at about 20 ° C. in solution.
About 300 ° C., preferably about 150 ° C. to about 200 ° C.,
More preferably, it is performed at a temperature of about 160C to about 165C. Preferably, the polymerization is performed at much the same reaction temperature and using the same initiator or initiators. The initiator should be selected such that its half-life at the reaction temperature is preferably within about 30 minutes, particularly preferably within about 5 minutes, and even more preferably within about 2 minutes. Particularly preferred are initiators having a half-life of less than about 1 minute at a temperature of about 150C to about 200C.
In general, if the initiator has a shorter half-life and / or if more initiator is used, more branched monomers can be included. Vinyl polymer excipients used in the ink preferably remain (unreacted)
Has little or no monomer content. In particular, the vinyl excipient is preferably substantially free of residual monomers, i.e., less than about 0.5% by weight of residual monomers, based on the total weight of the monomers to be polymerized, and more preferably Has less than about 0.1% residual monomer.

In the semi-batch process, the monomers and initiator are added to the polymerization reactor over a period of time, preferably at a constant rate. Typically, the addition time is from about 1 to about 10 hours, and an addition time of from about 3 to about 5 hours is common. Longer addition times produce smaller number average molecular weights. Lower number average molecular weights can also be produced by increasing the solvent to monomer ratio or by using stronger solvents for the resulting polymer.

Generally, the branched vinyl polymers used in the inks have a low number average molecular weight and a wide polydispersity. The number average molecular weight and weight average molecular weight of the vinyl resin used in the ink can be determined by gel permeation chromatography using polystyrene standards available for weight average molecular weights up to 6 million according to well-accepted methods. Polydispersity is defined as the ratio of M _w / M _n . In a preferred embodiment, the vinyl polymer has a number average molecular weight ( _Mn ) of at least about 1000, and more preferably at least about 2000.
The number average molecular weight is also preferably less than about 15,000, more preferably less than about 10,000, and even more preferably less than about 8500. A preferred range for _Mn is from about 1000 to about 10,000, and a more preferred range for _Mn is from about 2000 to about 8
500, and an even more preferred range is about 40
00 to about 8000. The weight average molecular weight should be at least about 30,000, preferably about 100,000. The weight average molecular weight ( _Mw ) is preferably up to about 600,000 based on GPC measurements using available standards having a weight average molecular weight of 6 million. A preferred range for M _w is from about 30,000 to about 55 million, and a more preferred range for M _w is from about 100,000 to
About one million, and an even more preferred range is from about 100,000 to about 300,000. About 100,0
For the M _w range from 00 to about 300,000, resins having ultra-high molecular weight shoulders (greater than about 45 million) observable by GPC should preferably be avoided. The polydispersity, ie the ratio of M _w / M _n , may be up to about 10,000, preferably up to about 1000. The polydispersity is preferably at least about 15, particularly preferably at least about 50. The polydispersity preferably falls within the range of about 15 to about 1000, and more preferably it is about 50 to about 80
It falls within the range of 0.

The theoretical glass transition temperature can be adjusted by the choice and proportion of comonomers according to methods known in the art. In a preferred embodiment, the theoretical T _g is above room temperature, and preferably the theoretical T _g is at least about 60 ° C, more preferably at least about 70 ° C. The methods and compositions of the present invention are preferably at about 50 ° C.
About 125 ° C, more preferably about 60 ° C to about 100 ° C
Of, and even more preferably to use a vinyl polymer having a T _g of about 70 ° C. ~ about 90 ° C..

In one embodiment of the single-fluid ink, an acid-functional vinyl polymer, which may be a branched vinyl polymer, is combined with another resin in the ink composition. Examples of other suitable resins that can be combined with the acid-functional vinyl polymer are polyester and alkyd resins, phenolic resins, rosins, cellulosics, and derivatives thereof, such as rosin-modified phenolic, phenolic -Modified rosins, hydrocarbon-modified rosins, maleic-modified rosins, fuma-based modified rosins; including, but not limited to, hydrocarbon resins, other acrylic or vinyl resins, polyamide resins, and the like. . Such resins or polymers may have a weight of about 6% based on the non-volatile weight of the resin.
Up to about 1 part by weight of the acid-functional vinyl polymer can be included.

[0052] In addition to the acid-functional vinyl resin and any optional second resin, the ink composition preferably includes one or more solvents. In a preferred embodiment of the single-fluid ink, the branched vinyl resin forms a solution having no apparent turbidity or a distinct solution in the solvent or solvents of the ink formulation. The particular solvent and the amount of solvent included will be determined by the desired ink viscosity, body, and tack. Generally, non-oxygenated solvents or solvents having a low Kauri-Butanol (KB) number are used for inks that will come into contact with parts, such as rubber rollers, during the lithographic process, and rubber To avoid affecting. Suitable solvents for the ink that will come into contact with the rubber part include, but are not limited to, aliphatic hydrocarbons, such as petroleum distillate fractions, and normal and isoparaffinic solvents having limited aromatic properties. For example, petroleum middle distillate fractions such as the Pennsylvania Refining Company of Franklin Park, Illinois
Vangie Refining Companny), a trademark of Maggie Sols, available from Maggie Bros. Oil Company, a subsidiary of Exxon Chemical Co., Houston, Texas. ) As the trademark ExxPrint, available from
Golden Bear Oil Specialties of Oildale, Total Petroleum Inc. of Denver, Colorado, and Calumet Labricanz of Indianapolis, Indiana
Those available from the company (Calumet Lubricants Co.) can be used. Additionally or alternatively, it may contain soybean oil or other vegetable oils.

For example, when using non-oxygenated solvents such as these, it is necessary to have sufficient affinity for the aliphatic solvent to obtain the desired solvency of the preferred branched vinyl polymer. It is generally necessary to include significant amounts of at least one monomer. Generally, acrylate monomers having at least 6 carbon atoms in the alcohol portion of the ester or styrene or alkylated styrene, such as tert-butylstyrene, are included in the monomers polymerized for this purpose. May be included. In a preferred embodiment, the ink composition with the non-oxygenated solvent has at least about 20%, preferably about 20% to
A branched chain polymerized from a monomer mixture comprising about 40%, and more preferably from about 20% to about 25%, of an aliphatic solubility enhancing monomer such as stearyl methacrylate or t-butylstyrene. Stearyl methacrylate is a preferred such monomer, including vinyl resins. At least about 55% styrene, preferably about 55%
% To about 80% styrene, and more preferably about 60%.
It is also preferred to include from about 70% to about 70% styrene. If desired, methyl methacrylate or other monomers can be used to reduce solvent resistance in aliphatic solvents.
All percentages are by weight based on the total weight of the monomer mixture to be polymerized. Among the preferred monomer compositions for vinyl polymers for lithographic inks are (meth) acrylates of alcohols having 8-20 carbon atoms, such as stearyl methacrylate, styrene, divinylbenzene, and (meth) acrylic acid. Are included. In a preferred embodiment, the branched vinyl for lithographic inks comprises from about 15, preferably from about 20 to about 30, preferably up to about 25% by weight of a (meth) acrylic acid ester of an alcohol having 8 to 20 carbon atoms, especially methacrylic acid. About 50, preferably about 60 to about 80, preferably up to about 75% by weight of the styrenic monomer, especially styrene itself; divinylbenzene in an amount as indicated above; and about 0.5, Preferably from about 2.5 to about 5, preferably up to about 4% by weight of acrylic acid or more preferably
Manufactured using methacrylic acid.

[0054] Preferably, the solvent or solvent mixture will have a boiling point of at least about 100 ° C and preferably no more than about 550 ° C. Offset printing inks can use solvents having a boiling point above about 200 ° C. Newsprint inks generally contain from about 20 to about 85% by weight of a solvent such as mineral oil, vegetable oil, and high boiling petroleum distillate,
Formulated with The amount of solvent will also vary depending on the type of ink composition (ie, whether the ink is newsprint, heatset, sheetfed, etc.), the particular solvent used, and other factors known in the art. Typically, the solvent content for lithographic inks is up to about 60%, which may include oil as part of the solvent package. Generally, at least about 35% of the solvent will be present in the lithographic ink. When used to formulate a preferred single-fluid ink composition, these varnishes or excipients, including branched vinyl resins, are typically clear, clear solutions.

[0055] The ink composition will generally include one or more pigments. The number and type of pigments will depend on the type of ink to be formulated.
Newsprint ink compositions will typically include only one or a small number of pigments, such as carbon black, but gravure inks may include more complex pigment packages and e.g. Alternatively, it may be prepared in multiple colors including a color having a special effect such as a metal effect. Lithographic printing inks are typically used in four colors: magenta, yellow, black, and cyan;
And can be formulated for pearlescent or metallic effect. Any of the common inorganic and organic pigments can be used in the ink compositions of the present invention. Alternatively, the composition can be used as an overprint lacquer or varnish. The overprint lacquer (air dried) or varnish (cured) is intended to be clear or transparent and therefore does not include opaque pigments.

The lithographic ink composition used in the present invention is preferably a monolith having a continuous oil-based phase containing an acid-functional vinyl excipient and a polyol discontinuous phase containing a liquid polyol. Formulated as a fluid ink. The vinyl polymer phase is relatively stable to the polyol phase. Stability is that the two phases do not separate in the fountain solution. However, during the application of the ink, the emulsion breaks and the polyol comes to the surface, moistening the areas of the plate that do not accept the ink. Inks that are stable in fountain solution, however, break off quickly and separate neatly on the print without toning and give constant transfer properties. Suitable stability may also depend on the particular acid-functional vinyl polymer and the particular polyol chosen. The acid number and molecular weight can be adjusted to give the desired stability.

Higher acid number vinyl resins can be used in smaller amounts, but the acid number must not be too high or the vinyl polymer will not be sufficiently soluble in hydrocarbon solvents. . Generally, an increase in the acid number of the acid-functional vinyl resin will be accompanied by a decrease in the amount of such resin included in the hydrophobic phase.

Polyethylene glycol oligomers such as diethylene glycol, triethylene glycol,
And tetraethylene glycol, and ethylene glycol, propylene glycol, and dipropylene glycol are examples of preferred liquid polyols for the polyol phase of the single-fluid ink used in the present invention. The polyol phase includes, of course, a mixture of different liquid polyols. Generally, lower acid number vinyl or acrylic polymers are used with higher molecular weight polyols. The polyol phase can include other substances. A weak acid, such as citric acid, tartaric acid, or tannic acid, or a weak base, such as triethanolamine, can be included in an amount from about 0.01% to about 0.5% by weight of the ink composition. Certain salts, such as magnesium nitrate, may be present in an amount of about 0.01% to about 0.5% by weight, based on the weight of the ink composition.
Preferably, an amount of about 0.08 to about 1.5% by weight can be included to help protect the plate and extend plate life. Wetting agents, such as polyvinylpyrrolidone, may be added to help wet the plate. About 0.5% to about 1.5% by weight, based on the weight of the ink composition, of polyvinylpyrrolidone is included.

The single-fluid ink is used in an amount of about 5% to about 50%, preferably about 10% to about 35%, and particularly preferably about 20% to about 50%, based on the total weight of the ink composition.
About 30% can be formulated with the polyol phase. Unless another means for cooling is provided, a sufficient amount of the polyol is preferably present in the ink composition to keep the plate at a operable low temperature. The amount of polyol phase required for good toning and printing depends on the type of plate used and can be determined by simple tests. Up to about 4 or 5% by weight of water may be included in the polyol phase mixture to help dissolve or homogenize the components of the polyol phase.

Other additives known in the art that may be included in the ink compositions used in the present invention will be known to those skilled in the art, provided that the additives do not significantly reduce the advantages of the present invention. . Illustrative examples of these are pour point depressants, surfactants, wetting agents, waxes, emulsifiers and dispersants, antifoams, antioxidants, UV absorbers, desiccants (eg,
(Including formulations containing vegetable oils), flow agents and other rheology modifiers, gloss enhancers, and anti-precipitants. When included, additives typically comprise at least about 0.001% of the ink composition.
And may be included in amounts of about 7% or more by weight of the ink composition. Supply Roll The lithographic base is automatically supplied to the printing machine cylinder by unwinding the base from a supply spool or from a supply roll, ie, the web of lithographic base wound on the supply spool. The unwound lithographic base is wound around a printing machine cylinder, which is preferably a plate cylinder that holds the printing master during printing. The supply roll is preferably EP-
A 640 478, as described in the plate cylinder. Alternatively, the supply roll can be arranged outside the cylinder and then the unrolled lithographic base can be wound around the cylinder and preferably cut from the web on the supply roll. After printing, the used material is preferably wound up on a take-up roll or spool, which is also preferably integrated in the cylinder. Technical details of a preferred embodiment of such an integrated supply and take-up roll and the associated drive and tension adjustment mechanism can be found in EP-A 640 478. Coating step The image-recording layer is transferred from the donor material by heat- or friction-induced transfer as described in EP 1 048 458 or, for example, from EP-A 974 455 and 99.
EP-A-9920368 filed on November 3, 2015
2 by powder coating or by known coating methods such as spin-coating, zip coating, rod coating, blade coating, air knife coating,
It can be applied by coating a liquid solution according to gravure coating, reversing roll coating, extrusion coating, slide coating, and curtain coating. A review of these coating technologies can be found in the book "Modern Coating and Drying Technolo
gy ", Edward Cohen and Edgar B. Gutoff Editors, VCH
Publishers, Inc, New York, NY, 1992. The coating solution can also be applied to the substrate by a printing technique, such as ink-jet printing, gravure printing, flexographic printing, or offset printing.
EP-A No. 00020 filed on Jul. 31, 2000
The injection described at 700 is very preferred.

According to another very preferred embodiment, the coating solution is sprayed onto the substrate by means of a head comprising a spray nozzle. Preferred values for the spray parameters are EP-A No. 9 both filed on Sep. 15, 1999.
9203064 and EP-A No. 99206565. In a preferred arrangement, the spray head moves axially along the lithographic base while the cylinder of the printing machine rotates in an angled direction.

Spraying or spray coating is a preferred technique for applying an image-recording layer comprising thermoplastic polymer particles or an aryldiazosulfonate polymer, as described above. Exposure Step The imaging material used in the present invention is exposed to heat or light on-press, i.e., while the material is placed on a printing machine cylinder, preferably a plate cylinder that holds the print master during printing. Is done. The exposure can be performed by, for example, a thermal head, an LED, or a laser head. Preferably, 1
One or more lasers are used, for example He / Ne lasers, Ar lasers or UV laser diodes. Most preferably, sunlight-stable materials can be used because the light used for exposure is not visible light, such as ultraviolet (laser) light or near infrared having a wavelength in the range of about 700 to about 1500 nm. Light-generating lasers, for example semiconductor laser diodes, Nd: YA
G or Nd: YLF laser is used. The required laser power is the sensitivity of the image-recording layer, the pixel dwell time of the laser beam as measured by the spot diameter (typical value of a modern plate-setter at a maximum intensity of 1 / e ² : 20-25 μm), the scanning speed. And the resolution of the exposure device (ie, the number of addressable pixels per linear distance, often expressed in dots per inch or dpi, typical values: 1000-4000 dp
i). Further technical details of the on-press exposure device are described, for example, in US 5,174,205 and U.S. Pat.
S 5,163,368. Processing Step After exposure, the image-recording layer is processed by supplying the single-fluid ink, preferably by means of an inking roller of a printing machine, which supplies the ink to the plate cylinder. Preferably,
The same single-fluid ink is used for the processing and subsequent printing steps. In that embodiment, the processing and printing steps are part of the same operation, and after exposure, the printing process is started by applying a single-fluid ink to the material and the first few revolutions of the printing press cylinder (typically After less than 20 times, more preferably less than 10 times), the imaging layer is completely processed and subsequently a high quality printed copy is obtained throughout the operation of the printing press. As explained above, areas of the image-recording layer that are soluble in the single-fluid ink or made solubilized in the single-fluid ink by the exposure step are removed during the processing step. Preferably, the removed components are transferred to printing paper.

Treatment of the imaging element with a single-fluid ink involves first wetting or swelling the image-recording layer with a supply of water or an aqueous liquid, thereby substantially eliminating the image-recording layer.
It is possible to proceed with a free selection step in which the recording layer is not removed.

[0064]

EXAMPLES 1. Production of vinyl varnish Ketrul 220 (Total Petroleum Inc.) in an amount of 44.19 parts by weight
(Roleum, Inc.) is charged to a glass reactor equipped with a stirrer, nitrogen inlet, total reflux condenser, and monomer inlet. The solvent is heated to 160 ° C. under a nitrogen atmosphere while stirring. 36.
01 parts by weight styrene, 12.27 parts by weight stearyl methacrylate, 2.62 parts by weight divinylbenzene, 1.
89 parts by weight of methacrylic acid and 2.79 parts by weight of t
A monomer mixture of -butylperoxyisopropyl carbonate (75% solution in mineral spirits) is added to the reactor over a period of 3 hours. After the monomer addition is complete, 0.23 parts by weight of t-butyl peroxyisopropyl carbonate are added over a period of 15 minutes. The temperature is maintained at 160 ° C. for a further 2 hours to completely convert the monomer to polymer.

The measured amount of non-volatiles (NVM) is 55%. The conversion, measured as NVM divided by the percentage of the total weight of the monomers, is 100.1. The acid number for the solution is 12.0 mg KOH / gram
It is. Viscosity is 30 strokes (bubble tube, 5
4.4 ° C). The solvent resistance is 230% and the NVM at the cloud point is 16.7%. 2. Preparation of a single-fluid ink 58.0 grams of the following mixture A are added to 142.0 grams of the following mixture B with stirring. Ink composition 2
While maintaining the vortex on the disperser for 0 minute and 6 minutes
Mix while maintaining the temperature below 0 ° C. The ink composition has a single fall time Laray of 14-17 seconds at 30C for 500 grams. Mixture A : 181 in glass beaker until clear.
0 grams of diethylene glycol, 8.0 grams of water,
Mix 0.4 grams citric acid and 0.4 grams magnesium nitrate. Add 191.2 grams of diethylene glycol and mix until homogeneous. Mixture B : 46.0 grams of the above vinyl varnish, 4.0 grams of blue flash (Bl
ue Flush) 12-FH-320 (CDR Corporati, Elizabethtown, Kentucky)
1.0 g of industrial soybean oil (available from Cargill, Chicago, Ill.) and 0.6 g of an antioxidant. While mixing, 34.4 grams of the hydrocarbon resin solution (EXX-Print 283, available from Neville)
60% LX-2600 in D), 27.0 grams of carbon black (Cabot Cor.
p.), and 1.0 g of polytetrafluoroethylene wax (Carroll.
Add Pinnacle 9500D, available from Carrol Scientific). Mix at 149 ° C. for 30 minutes at high speed. Reduce mixing speed and 27.0 grams of EXX-Print 58
Add 8D (available from Exxon). The premix is milled in a shot mill to a suitable mill.

Mixture B had a Lalay viscosity of 180-240 poise and a Lalay yield of 800-1200 (Test Method A).
According to STM D4040: exponentiation-3k, 1.5k,
0.7k, 0.3k). Mixture B is tested on an Inkometer for 1 minute at 1200 rpm for a measured result of 25-29 units. 3. Lithographic base PET web having a thickness of 0.175 mm
5 from a 23.6% aqueous coating solution with H
Coating was performed with a wet coating thickness of 0 μm. 3
After cooling to 10 ° C. over 0 seconds, the layer was dried at a temperature of 50 ° C. with a moisture content of 4 g / m ³ of air for at least 3 minutes. The resulting hydrophilic base layer is 89
90 mg / m ² TiO ₂ , 900 mg / m ² SiO ₂ ,
990 mg / m ² polyvinyl alcohol, 81.6 mg
/ M ² of SAPONIN ^™ , 36.8 mg / m ² of HOSTAPON T ^™ and 605 mg / m ² of FT2
It contained 48 ^{T M.}

Saponin is a nonionic surfactant mixture consisting of esters and polyglycosides, which is commercially available from Merck. Hostapon T is an anionic surfactant commercially available from Hoechst AG. FT248 is an anionic perfluorosurfactant commercially available from Bayer AG.

The above TiO ₂ and SiO ₂ were added to the coating solution as a dispersion in polyvinyl alcohol.
The TiO ₂ dispersion had an average particle size between 0.3 and 0.5 μm. Polyvinyl alcohol is a hydrolyzed polyvinyl acetate marketed under the trademark POLYVIOL WX ^™ by Wacker Chemie GmbH, Germany. The above SiO ₂ was added as a dispersion of hydrolyzed tetramethyl orthosilicate. 4. Image-Recording Layer A 2.61% by weight aqueous solution was prepared by mixing a polystyrene latex, a heat absorbing compound and a hydrophilic binder. This solution was coated on the hydrophilic base layer of the PET support described above. After drying, the image-recording layer has a thickness of 0.83 μm and 75% by weight of polystyrene latex, 10% by weight of infrared dye IR-1 and 15% by weight of polyacrylic acid as hydrophilic binder (NV Allie
d Colloids Belgium)
ascol) E15).

[0069]

Embedded image

The above solution was sprayed on a lithographic base. For this purpose, the lithographic base was placed on a body rotating at a linear speed of 164 m / min. The imaging element was coated by a spray nozzle moving at a speed of 1.5 m / min in the axial direction of the cylinder. Spray nozzle is 40m between nozzle and base
m. The flow rate of the spray solution was set at 7 ml / min. During the spraying process, 90 psi air pressure was used on the spraying head. The coating was dried during the spraying process at an air temperature of 70 ° C.

The spray nozzle used was Spraying Systems Bergium, Brussels.
Belgium), type SUV76, an air assisted spray nozzle. 5. Exposure, processing and printing The imaging material described above was prepared using an external drum platesetter (830 nm) mounted on the printing cylinder of a modified KORD 64 printing machine from Heiderberger Druckmaschinen, Germany. , 2400d
pi, a surface linear velocity of 1 m / s and a power setting of 16 watts). After exposure, the printing press was started and the single-fluid ink described above was applied to the image-recording layer. After ten revolutions, the processing phase was completed and the paper feed was started. A clean print without ink absorption in the non-image areas was obtained.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Eric Bercyuelen Belgium B 2640 Maltcell Septes Trat 27 Agfa-Gevert Na Mrose Fennoutjaps 2640 Maltcell Septes Trat 27 Agfa-Gevert na Murose Fennoutjap (72) Inventor Giyoan Belmercille Belgium B 2640 Maltcell Septes Trat 27 Agfa-Gevert na Mlose Huennoutjapp (72) Inventor Ruday Gade Wake Belgium Bee 2640 Malt Cell Septes Trat 27 Agfa-Gevert na Muro And non-end notebook Shea guy-flops in the F-term (reference) 2H025 AB03 AC08 AD01 BA00 CB51 CB54 CC20 FA03 2H084 AA14 BB02 BB04 CC05 2H096 AA07 AA08 BA16 BA20 CA20 EA04 2H114 AA04 AA28 BA02 DA08 DA25 DA48 DA51 DA52 EA01

Claims (10)

[Claims] 1. A web of a flexible lithographic base having a hydrophilic surface is unwound from a supply spool, (ii) the lithographic base is wrapped around the cylinder of a printing machine, and (iii) a single-fluid ink. An image that can be removed in a single-fluid ink or removable by exposure to heat or light
Applying the recording layer on a lithographic base, (iv) exposing the image-recording layer imagewise to heat or light, and (v) treating the image-recording layer by supplying a single-fluid ink; Thereby obtaining a print master, (vi) printing by supplying a single-fluid ink to a print master located on a plate cylinder of a printing machine, and (vii) removing the print master from the plate cylinder. Lithographic printing method. 2. A non-ablationable image in which the image-recording layer is removable with a single-fluid ink prior to exposure to heat or light and less removable by exposure to heat or light. The method according to claim 1, which is a recording layer. 3. The method according to claim 2, wherein the image-recording layer comprises hydrophobic thermoplastic polymer particles. 4. The method according to claim 3, wherein the image-recording layer further comprises a hydrophilic binder. 5. The method according to claim 2, wherein the image-recording layer comprises an aryldiazosulfonate polymer. 6. The method according to claim 1, wherein the supply spool is arranged in the plate cylinder. 7. The method according to claim 1, wherein step (vii) is carried out by winding the print master onto a take-up spool arranged in a plate cylinder. 8. A flexible lithographic base comprising a plastic support, a thin aluminum support or a laminate of plastic and thin aluminum.
The method according to any of the above. 9. A method according to claim 1, wherein the single-fluid ink is an emulsion comprising: a continuous phase comprising an acid-functional vinyl resin; and a discontinuous phase comprising a liquid polyol. The method described in Crab. 10. The method according to claim 10, wherein the vinyl resin is about 1000 to about 1500.
A number average molecular weight between 0 and at least about 100,000
A process according to claim 9, which is a branched acid-functional vinyl resin having a weight average molecular weight of