EP1065051A1 - Processless printing plate with cover layer containing compounds with cationic groups - Google Patents
Processless printing plate with cover layer containing compounds with cationic groups Download PDFInfo
- Publication number
- EP1065051A1 EP1065051A1 EP19990202110 EP99202110A EP1065051A1 EP 1065051 A1 EP1065051 A1 EP 1065051A1 EP 19990202110 EP19990202110 EP 19990202110 EP 99202110 A EP99202110 A EP 99202110A EP 1065051 A1 EP1065051 A1 EP 1065051A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- heat
- sensitive material
- layer
- material according
- hydrophilic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C1/00—Forme preparation
- B41C1/10—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme
- B41C1/1008—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by removal or destruction of lithographic material on the lithographic support, e.g. by laser or spark ablation; by the use of materials rendered soluble or insoluble by heat exposure, e.g. by heat produced from a light to heat transforming system; by on-the-press exposure or on-the-press development, e.g. by the fountain of photolithographic materials
- B41C1/1033—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by removal or destruction of lithographic material on the lithographic support, e.g. by laser or spark ablation; by the use of materials rendered soluble or insoluble by heat exposure, e.g. by heat produced from a light to heat transforming system; by on-the-press exposure or on-the-press development, e.g. by the fountain of photolithographic materials by laser or spark ablation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/36—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using a polymeric layer, which may be particulate and which is deformed or structurally changed with modification of its' properties, e.g. of its' optical hydrophobic-hydrophilic, solubility or permeability properties
- B41M5/368—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using a polymeric layer, which may be particulate and which is deformed or structurally changed with modification of its' properties, e.g. of its' optical hydrophobic-hydrophilic, solubility or permeability properties involving the creation of a soluble/insoluble or hydrophilic/hydrophobic permeability pattern; Peel development
Definitions
- the present invention relates to a heat mode recording material for making a lithographic plate for use in lithographic printing.
- the present invention further relates to a method for imaging said heat mode recording material e.g. by means of a laser.
- Lithographic printing is the process of printing from specially prepared surfaces, some areas of which are capable of accepting ink (oleophilic areas) whereas other areas will not accept ink (hydrophilic areas).
- oleophilic areas areas of which are capable of accepting ink
- hydrophilic areas areas of which are capable of accepting ink
- hydrophilic areas are applied to the plate surface that contains hydrophilic and oleophilic areas.
- the hydrophilic areas will be soaked with water or the dampening liquid and are thereby rendered oleophobic while the oleophilic areas will accept the ink.
- DE-A- 2 448 325 discloses a laser heat mode "direct negative" printing plate comprising e.g. a polyester film support provided with a hydrophilic surface layer.
- the disclosed heat mode recording material is imaged using an Argon laser thereby rendering the exposed areas oleophilic.
- An offset printing plate is thus obtained which can be used on an printing press without further processing.
- the plate is called a "direct negative” plate because the areas of the recording material that have been exposed are rendered ink accepting.
- DE-A- 2 448 325 concern "direct negative" printing plates comprising e.g. hydrophilic aluminium support coated with a water soluble laser light (Argon-488nm) absorbing dye or with a coating based on a mixture of hydrophilic polymer and laser light absorbing dye (Argon - 488nm).
- heat mode recording materials for preparing "direct negative” printing plates include e.g. US-A- 4 341 183, DE-A- 2 607 207, DD-A- 213 530, DD-A- 217 645 and DD-A- 217 914 . These documents disclose heat mode recording materials that have on an anodized aluminium support a hydrophilic layer.
- the disclosed heat mode recording materials are image-wise exposed using a laser.
- Laser exposure renders the exposed areas insoluble and ink receptive, whereas the non exposed image portions remain hydrophilic and water soluble allowing to be removed by the dampening liquid during printing exposing the hydrophilic support.
- Such plates can be used directly on the press without processing.
- DD-A- 155 407 discloses a laser heat mode "direct negative" printing plate where a hydrophilic aluminum oxide layer is rendered oleophilic by direct laser heat mode imaging. These printing plates may also be used on the press without further processing.
- EP-A- 580 393 discloses a lithographic printing plate directly imageable by laser discharge, the plate comprising a topmost first layer and a second layer underlying the first layer wherein the first layer is characterized by efficient absorption of infrared radiation and the first and second layer exhibit different affinities for at least one printing liquid.
- EP-A- 683 728 discloses a heat mode recording material comprising on a support having an ink receptive surface or being coated with an ink receptive layer a substance capable of converting light into heat and a hardened hydrophilic surface layer having a thickness not more than 3 ⁇ m. The lithographic properties of said material are not very good.
- a heat-sensitive material for making lithographic plates comprising in the order given on a support an IR-sensitive oleophilic layer and a cross-linked hydrophilic layer, characterized in that said heat-sensitive material is covered with a layer comprising at least an organic compound comprising cationic groups.
- the organic compounds having cationic groups for use in connection with the present invention are preferably hydrophilic and may be low moleculair weight compounds but are preferably polymers.
- Preferred compounds are those having one or more ammonium groups or amino groups that can be converted to ammonium groups in an acidic medium.
- An especially preferred type of cationic compounds are polysacharides modified with one or more groups containing an ammonium or amino group.
- Most preferred organic compounds having cationic groups are dextrans or pullulan wherein at least some of the hydroxy groups have been modified into one or more of the following groups: -O-R 1 -O-CO-R 2 wherein R 1 represents an organic residue containing an amino or ammonium group, e.g. an amine substituted alkyl, an amine substituted alkylaryl etc..
- R 2 has one of the significances given for R 1 or stands for -OR 3 or -N(R 4 )R 5 , wherein R 3 has one of the significances given for R 1 and each of R 4 and R 5 which may be the same or different and have one of the significances given for R 1 .
- Pullulan is a polysacharide that is produced by microorganisms of the Aureobasidium pullulans type (Pullularia pullulans) and that contains maltotriose repeating units connected by a a-1,6 glycosidic bond. Pullulan is generally produced on industrial scale by fermentation of partially hydrolysed starch or by bacterial fermentation of sucrose. Pullulan is commmercially available from e.g. Shodex, Pharmacosmos.
- dextrans or pullulan suitable for use in accordance with the present invention are dextrans or pullulan wherein some of the hydroxyl groups have been modified in one of the groups shown in table 1.
- the modified dextrans or pullulan can be prepared by a reaction of a dextran with e.g. alkylating agents, chloroformates, acid halides, carboxylic acids etc...
- the organic compound having one or more cationic groups according to the invention is preferably provided in an amount of 10 to 2000 mg/m 2 and more preferably in an amount of 20 to 1000 mg/m 2 .
- hydrophilic coatings are preferably cast from aqueous compositions containing hydrophilic binders having free reactive groups including e.g. hydroxyl, carboxyl, hydroxyethyl, hydroxypropyl, amino, aminoethyl, aminopropyl, carboxymethyl, etc., along with suitable crosslinking or modifying agents including e.g. hydrophilic organotitanium reagents, aluminoformyl acetate, dimethylol urea, melamines, aldehydes, hydrolyzed tetraalkyl orthosilicate, etc..
- hydrophilic organotitanium reagents e.g. hydrophilic organotitanium reagents, aluminoformyl acetate, dimethylol urea, melamines, aldehydes, hydrolyzed tetraalkyl orthosilicate, etc.
- Suitable polymers for hydrophilic layers may be selected from the group consisting of gum arabic, casein, gelatin, starch derivatives, carboxymethyl cellulose and Na salt thereof, cellulose acetate, sodium alginate, vinyl acetate-maleic acid copolymers, styrene-maleic acid copolymers, polyacrylic acids and salts thereof, polymethacrylic acids and salts thereof, hydroxyethylene polymers, polyethylene glycols, hydroxypropylene polymers, polyvinyl alcohols, and hydrolyzed polyvinylacetate having a hydrolyzation degree of at least 60% by weight and more preferably at least 80% by weight.
- Hydrophilic layers containing polyvinylalcohol or polyvinylacetate hydrolyzed to an extent of at least 60% by weight hardened with a tetraalkyl orthosilicate, e.g. tetraethyl orthosilicate or tetramethyl orthosilicate, as disclosed in e.g. US-P- 3 476 937 are particularly preferred because their use in the present heat mode recording material results in excellent lithographic printing properties.
- a further suitable hardened hydrophilic surface layer is disclosed in EP-A- 514 990 .
- the hydrophilic layer disclosed in this EP-application comprises the hardening reaction product of a (co)polymer containing amine or amide functions having at least one free hydrogen (e.g. amino modified dextrane) and aldehyde.
- a cross-linked hydrophilic binder in the heat-sensitive layer used in accordance with the present embodiment preferably also contains substances that increase the mechanical strength and the porosity of the layer e.g. metal oxide particles which are particles of titanium dioxide or other metal oxides. Incorporation of these particles gives the surface of the cross-linked hydrophilic layer a uniform rough texture consisting of microscopic hills and valleys.
- these particles are oxides or hydroxydes of beryllium, magnesium, aluminium, silicon, gadolinium, germanium, arsenic, indium, tin, antimony, tellurium, lead, bismuth or a transition metal.
- Particularly preferable particles are oxides or hydroxides of aluminum, zirconium, silicon and titanium, used in 20 to 95 % by weight of the hydrophilic layer, more preferably in 30 to 90% by weight of the hydrophilic layer.
- the cross-linked hydrophilic layer is preferably coated at a dry thickness of 0.3 to 5 ⁇ m, more preferably at a dry thickness of 0.5 to 3 ⁇ m.
- the hardened hydrophilic layer may comprise additional substances such as e.g. plasticizers, pigments, dyes etc.
- the cross-linked hydrophilic layer can additionally contain an IR-absorbing compound in order to increase the IR-sensitivity.
- the IR-sensitive oleophilic layer comprises an oleophilic binder and a compound capable of converting light into heat.
- Suitable compounds capable of converting light into heat are preferably infrared absorbing components having an absorption 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 as disclosed in EP-A- 908 307 and pigments and in particular infrared pigments such as 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 .
- conductive polymer dispersion such as polypyrrole or polyaniline-based conductive polymer dispersions.
- the lithographic performance and in particular the print endurance obtained depends i.a.on the heat-sensitivity of the imaging element. In this respect it has been found that carbon black yields very good and favorable results.
- the oleophilic polymer is selected from the group consisting of polyvinyl chloride, polyesters, polyurethanes, novolac, polyvinyl carbazole etc., copolymers or mixtures thereof.
- the polymeric binder in the recording layer is heat sensitive: e.g. a polymer containing nitrate ester groups (e.g. self oxidizing binder cellulose nitrate as disclosed in GB-P- 1 316 398 and DE-A- 2 512 038) ; e.g. a polymer containing carbonate groups (e.g. polyalkylene carbonate); e.g. a polymer containing covalently bound chlorine (e.g. polyvinylidene chloride).
- substances containing azo or azide groups capable of liberating N 2 upon heating are favourably used.
- the oleophilic layer is coated at a dry weight from 0.5 to 30 g/m 2 , preferably from 3 to 15 g/m 2 .
- the support according to the present invention is preferably dimensionally stable and can be aluminum or another metal or alloy.
- Preferentially electrochemically and/or mechanically grained and anodised aluminum is used in the present invention..
- the support can be a flexible support.
- flexible support in connection with the present embodiment it is particularly preferred to use a plastic film e.g. substrated polyethylene terephthalate film, polyethylene naphthalate film, cellulose acetate film, polystyrene film, polycarbonate film, polyethylene film, polypropylene film, polyvinyl chloride film, polyether sulphone film.
- the plastic film support may be opaque or transparent.
- the plastic film is preferably subbed with subbing layers as described i n EP-A- 619 524, EP-A- 619 525 and EP-A- 620 502 .
- Still further paper or glass of a thickness of not more than 1.2 mm can also be used.
- the imaging element is image-wise exposed.
- the cover layer and the cross-linked hydrophilic layer can be removed and said areas are converted to oleophilic areas while the unexposed areas remain hydrophilic.
- This is mostly the case when using short pixel dwell times (for example 1 to 100 ns).
- longer pixel dwell times for example 1 to 20 us
- the hydrophilic layer is not or only partially removed.
- the remaining parts of the hydrophilic layer can be removed on the press by contact with fountain solution and ink or by an additional wet or dry processing step between the IR-laser exposure and the start-up of the printing process.
- 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.
- a laser or L.E.D Preferably used are lasers that operate in the infrared or near-infrared, i.e. wavelength range of 700-1500 nm. Most preferred are laser diodes emitting in the near-infrared with an intensity greater than 0.1 mW/ ⁇ m 2 .
- the plate is then ready for printing without an additional development and can be mounted on the printing press.
- the imaging element is first mounted on the printing cylinder of the printing press and then image-wise exposed directly on the press. Subsequent to exposure, the imaging element is ready for printing.
- the printing plate of the present invention can also be used in the printing process as a seamless sleeve printing plate.
- the printing plate is soldered in a cylindrical form by means of a laser.
- This cylindrical printing plate which has as diameter the diameter of the print cylinder is slid on the print cylinder instead of mounting a conventional printing plate. More details on sleeves are given in "Grafisch Nieuws" , 15, 1995, page 4 to 6.
- the IR-sensitive layer On top of an aluminum substrate was coated the IR-sensitive layer to a wet coating thickness of 50 pm from a solution having the following composition:
- the hydrophilic layer was coated to a wet coating thickness of 20 ⁇ m from a solution having the following composition
- Element 6 On top of the imaging element, as described in the reference element, was coated a hydrophylic layer from a 1%w/w solution in water from a diethylaminoethoxylated dextran (DormacidTM from Pfeifer& Langen) This hydrophilic layer was coated to a dry thickness of 0.05 g/m 2 (element 1), 0.1 g/m 2 (element 2), 0.25 g/m 2 (element 3), 0.50 g/m 2 (element 5, 0.75 g/m 2 (element 5).
- Element 6 was prepared as follows: The imaging element as described in the reference element was treated with a 1 %w/w solution in water of DormacidTM by rinsing with a cotton pad soaked in the described solution.
- the resulting imaging elements were imaged on a Creo 3244 TrendsetterTM at 2400 dpi operating at a drum speed of 80 rpm and a laser output of 15.5 Watt
- the plate was mounted on a GTO 52 press using K+E 800 as ink and rotamatic as fountain solution.
- the press was started by allowing the print cylinder with the imaging element mounted thereon to rotate.
- the dampener rollers of the press were first dropped on the imaging element so as to supply dampening liquid to the imaging element and after 10 revolutions of the print cylinder, the ink rollers were dropped to supply ink. After 10 further revolutions paper was feeded.
- the Dmin and the dot area of the 50% screen at 200 lpi were measured at prints 5, 25 and 50 with a Macbeth RD918-SB.
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- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Thermal Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Printing Plates And Materials Therefor (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Materials For Photolithography (AREA)
Abstract
Description
no. | modified group |
1 | -O-CH2-CH2-NH2 |
2 | -O-CO-NH-CH2-CH2-NH2 |
3 | -O-CO-NH-CH2-CH2-N(CH2-CH2-NH2)2 |
4 | -O-CH2-CH2-NH-CH2-CH2-NH2 |
5 | -O-CH2-CH2-NH-CH2-CHOH-CH2-N+(CH3)3 Cl- |
6 | -O-(CH2-CH2-O)n-CH2-CH2-NH2 wherein n represents an integer from 1 to 50 |
7 | -O-CO-NH-CH2-CH2-NH-CH2-CHOH-CH2-N+(CH3)3 Cl- |
8 | -O-CH2-CH2-N(CH2-CH3)2 .HCl |
9 | -O-CH2-CH2-N(CH2-CH2-NH2)2 |
10 | -O-CONH-CH2-CH2-N(CH2-CH2-NH2)2 |
11 | -O-CONH-(CH2-CH2-O)n-CH2-CH2-NH2 |
- 279.3g
- Carbon black dispersion of the following composition
34.9 g Special Schwarz™ (Degussa)
3.5 g Nitrocellulose E950™ (Wolf Walsrode)
4.2 g Dispersing agent
236.7 g Methyl ethyl ketone - 217.8g
- Nitrocellulose solution of the following composition
21.8 g Nitrocellulose E950™
196.0 g Ethylacetate - 24.0g
- Cymel solution of the following composition
4.8 g Cymel 301™
19.2 g Ethylacetate - 8.75g
- p-toluene sulphonic acid solution of the following
composition
0.875 g p-toluene sulphonic acid
7.875 g Ethylacetate
- 70.0g
- TiO2- dispersion in water, stabilized with Polyviol WX 48™ (polyvinyl alcohol from Wacker) (10 % w/w polyvinyl alcohol versus TiO2) average particle size 0.3 to 0.5 µm)-6.25% w/w
- 30.0g
- hydrolyzed tetramethyl orthosilicate in water/ethanol-6.25% w/w
- 1.2g
- wetting agent in water-5%w/w
Element 6 was prepared as follows:
The imaging element as described in the reference element was treated with a 1 %w/w solution in water of Dormacid™ by rinsing with a cotton pad soaked in the described solution.
Drain of the elements | |||
Element | Page 5 | Page 25 | Page 50 |
Reference | 0.16 | 0.09 | 0.04 |
1 | 0.01 | 0.00 | 0.01 |
2 | 0.00 | 0.01 | 0.00 |
3 | 0.01 | 0.00 | 0.00 |
4 | 0.00 | 0.00 | 0.01 |
5 | 0.01 | 0.01 | 0.00 |
6 | 0.00 | 0.01 | 0.01 |
Dot area of a 50% screen at 200 1pi | |||
Element | Print 5 | Print 25 | Print 50 |
Reference | 90 | 91 | 89 |
1 | 70 | 71 | 72 |
2 | 70 | 72 | 73 |
3 | 71 | 69 | 70 |
4 | 72 | 72 | 71 |
5 | 71 | 69 | 72 |
6 | 70 | 72 | 72 |
Claims (9)
- A heat-sensitive material for making lithographic plates comprising in the order given on a support an IR-sensitive oleophilic layer and a cross-linked hydrophilic layer, characterized in that said heat-sensitive material is covered with a layer comprising at least an organic compound comprising cationic groups.
- A heat-sensitive material according to claim 1 wherein said organic compound is a hydrophylic polymer having one or more ammonium groups or a low molecular weight hydrophylic organic compound having one or more ammonium groups.
- A heat-sensitive material according to claim 2 wherein said hydrophilic polymer is a polysaccharide.
- A heat-sensitive material according to claim 3 wherein said polysaccharide is dextran or pullulan.
- A heat-sensitive material according to any of claims 1 to 4 wherein said organic compound is comprised in said imaging element in an amount between 0.01 and 2.00 g/m2.
- A heat-sensitive material according to any of claims 1 to 5 wherein said oleophilic layer is coated at a dry weight from 0.75 to 15 g/m2.
- A heat-sensitive material according to any of claims 1 to 6 wherein said cross-linked hydrophilic layer comprises oxides or hydroxydes of beryllium, magnesium, aluminium, silicon, gadolinium, germanium, arsenic, indium, tin, antimony, tellurium, lead, bismuth, titanium or a transition metal.
- A heat-sensitive material according to any of claims 1 to 7 wherein the hydrophilic layer has a dry thickness between 0.3 and 5 µm.
- A method for making lithographic printing plates comprising the steps of(i) image-wise exposing to a laser beam having an intensity greater than 0.1 mW/µm2 a heat sensitive material according to any of claims 1 to 8; (ii) before or after step (i) mounting the plate on a printing press; (iii) contacting said plate with fountain solution and ink.
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP19990202110 EP1065051B1 (en) | 1999-06-29 | 1999-06-29 | Processless printing plate with cover layer containing compounds with cationic groups |
DE69911933T DE69911933T2 (en) | 1999-06-29 | 1999-06-29 | Processing-free planographic printing plate with a cover layer which contains compounds containing cationic groups |
US09/599,966 US6399276B1 (en) | 1999-06-29 | 2000-06-23 | Processless printing plate with cover layer containing compounds with cationic groups |
JP2000194256A JP2001047758A (en) | 1999-06-29 | 2000-06-28 | Processless printing plate having coating layer containing compound having cationic group |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP19990202110 EP1065051B1 (en) | 1999-06-29 | 1999-06-29 | Processless printing plate with cover layer containing compounds with cationic groups |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1065051A1 true EP1065051A1 (en) | 2001-01-03 |
EP1065051B1 EP1065051B1 (en) | 2003-10-08 |
Family
ID=8240385
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19990202110 Expired - Lifetime EP1065051B1 (en) | 1999-06-29 | 1999-06-29 | Processless printing plate with cover layer containing compounds with cationic groups |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP1065051B1 (en) |
JP (1) | JP2001047758A (en) |
DE (1) | DE69911933T2 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7198883B2 (en) | 2004-09-24 | 2007-04-03 | Agfa-Gevaert | Processless lithographic printing plate |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3901565B2 (en) | 2002-04-15 | 2007-04-04 | 富士フイルム株式会社 | Heat sensitive planographic printing plate |
JP5455701B2 (en) * | 2010-02-19 | 2014-03-26 | 三菱製紙株式会社 | Thermal lithographic printing plate |
-
1999
- 1999-06-29 DE DE69911933T patent/DE69911933T2/en not_active Expired - Fee Related
- 1999-06-29 EP EP19990202110 patent/EP1065051B1/en not_active Expired - Lifetime
-
2000
- 2000-06-28 JP JP2000194256A patent/JP2001047758A/en not_active Withdrawn
Non-Patent Citations (1)
Title |
---|
No relevant documents disclosed * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7198883B2 (en) | 2004-09-24 | 2007-04-03 | Agfa-Gevaert | Processless lithographic printing plate |
Also Published As
Publication number | Publication date |
---|---|
EP1065051B1 (en) | 2003-10-08 |
JP2001047758A (en) | 2001-02-20 |
DE69911933T2 (en) | 2004-08-12 |
DE69911933D1 (en) | 2003-11-13 |
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