DE60107315T2 - Directly recordable planographic printing plates and process for their production - Google Patents

Description

The The present invention relates to a directly recordable planographic printing plate, made using a laser beam for direct plate making. In particular, this invention is effective in providing a directly writable, produce anhydrous planographic printing plate that allows Make prints without dampening water.

The Production of so-called directly recordable disks, the an offset printing plate directly from a block copy without required Using slides for plate making has many good ones Properties such as simplicity, which means no need more necessary to expertise, rapidity, creating a pressure plate can be made quickly, and rationality, allowing the selection of a desirable Systems from a wide range of printers depending on the required quality and available standing means becomes. With such good properties, this process has been largely in the areas of general offset printing and flexographic printing as well used in the area of small offset printing. Recently, in a row, the fast increasing availability improved dispensing systems, including preprinting systems, image setters and laser beam printers, in particular various new, directly writable Planographic printing plates developed. Directly writable planographic printing plates can regarding the mechanism used for plate making be divided into different groups. These methods can be laser beam irradiation, Thermal gradient to Imaging, pin electrodes for partial application of voltage or ink jet printing to form an ink repellent Use a layer or an ink-receptive layer. Under allows others the use of a laser beam increased image resolution and faster plate production, resulting in the availability of a variety Products of this type.

printing plates of the laser imaging type further divided into two subgroups: the photon type, the over light-induced reaction works, and the type of heat, the photothermal Conversion used to a heat reaction trigger. In particular, the products of the heat type are currently due to rapid improvement of semiconductor laser generators as a light source to mainstream products.

Various Methods have been proposed to provide heat-type planographic printing plates, in particular for anhydrous printing, which does not supply humidifying water while needed the printing process. However, all of these methods have various problems.

Some patents, such as USP 5,339,737, USP 5,353,705 and EP 0,580,393 Disclosed inventions relating to manufacturing methods for a printing plate based on grinding a heat-sensitive layer. Although advantageous in terms of ease of development, they require higher laser power to abrade the heat-sensitive layer, and gas or other by-products produced by abrading can adversely affect the optical system. In addition, additional operations for removing the abrasion residue are required, and it is difficult to reproduce small halftone dots.

One new printing plate type, in which the remaining heat-sensitive Layer is developed, for example, in EP-A-0.914.942 proposed. Such plates provided directly recordable, waterless planographic printing plates ready to produce high-quality prints, which is one of the most important properties of anhydrous printing, without showing negative effects on the optical system. These However, printing plates contain a heat-sensitive layer, the both in the laser-irradiated and in the non-irradiated Remains behind sections, due to the low contrast between the laser irradiated and the unirradiated portions when viewed optically leads to the problem difficult to check the plates. So there are difficulties in carrying out the review during the process after the Production of a printing plate until the beginning of the printing process and in terms of of possibly checking one Plate during of the printing process already attached to the printing device is. Such a check should before or during of printing confirm that the printing plate has been made as required. For this confirmation the plates are optically examined. This disk validation can fail in connection with data transmission from computers to the processing machine and errors during the Plate production can be stopped to manufacture due to to avoid this error of poor quality prints.

• (a) ein Verfahren zur Herstellung einer direkt beschreibbaren Flachdruckplatte nach Anspruch 1,
• (b) einen direkt beschreibbaren Flachdruckplattenvorläufer nach Anspruch 5 und
• (c) eine direkt beschreibbare Flachdruckplatte nach Anspruch 8 bereit.

The present invention according to the respective aspect

• (a) A method for producing a direct-write planographic printing plate according to claim 1,
• (b) a directly recordable planographic printing plate precursor according to claim 5 and
• (c) a directly recordable planographic printing plate according to claim 8 ready.

The The present invention is for the preparation of a directly writable Planographic printing plate through which it is possible is, such good features as high image rendering capability and to achieve simple disk verification operations.

embodiments The present invention will be described below in more detail.

The Production method of the invention for directly recordable planographic printing plates is characterized in that a laser beam is a directly writable Lithographic printing plate material irradiated, the at least one substrate, a heat sensitive Layer and an ink repellent layer in this order includes to the ink-repellent layer in the laser-irradiated Section, whereupon the inking of the printing area, the free of this ink repellent layer, followed by a dyeing solution. Furthermore, the invention is characterized in that the difference between the reflected absorption of the non-pressure area and the reflected absorption of the pressure range observed after dyeing the printing plate at the absorption maximum of the dye in the dyeing solution, not less than 0.3 and not more than 2.0. Herein refers to the Non-pressure area on the area where the ink-repellent Layer was not removed while the print area refers to the area in which the ink repellent Layer was removed.

The Production method of the invention for directly recordable planographic printing plates is characterized in that the heat-sensitive layer of Pressure range contains a dye having an absorption maximum within the range of visible light (400 nm to 700 nm) and that the difference between the reflected absorption the non-pressure area and the reflected absorption of the pressure area, observed at the absorption maximum of the dye, not less is less than 0.3 and not more than 2.0.

The fact that the dyeing of the developed area is effective for improving a lighter plate check is described in EP 0.914.942 however, the desired simplicity of disk inspection can not be achieved even if the disks are colored. The inventors of the present specification conducted conscientious studies and showed that the desired simplicity of plate inspection can be achieved when the difference between the reflected absorption of the non-printing area and the reflected absorption of the printing area observed at the absorption maximum of the dye used for dyeing is not less than 0.3. Dyeing is easier if the difference in absorption is not more than 2.0. The difference in the reflected absorption should preferably be not less than 0.5 and not more than 1.5. For ease of optical observation, the absorption maximum of the dye should preferably be in the range of visible light (400 nm to 700 nm). Even more preferred for the absorption maximum of the dye is a range of 500 nm to 650 nm to further enhance the simplicity of optical viewing and disk inspection.

The reflected absorption can be detected using an integration sphere with a spectrophotometer for the ultraviolet region and the visible region are measured. In particular, UV-Vis spectrophotometer U-3210 from Hitachi Ltd., equipped with an integration ball, can be used for measurement.

One Method for measuring the reflectance absorption of the pressure range is to make a sample containing only one pressure area and their reflected absorption with a UV-Vis spectrophotometer to eat. To increase the measurement accuracy, the sample should evenly with A laser beam is irradiated to the ink repellent Layer completely from a 1 cm × 1 cm large Remove section of the sample. A method of measuring the reflected Absorbance of the non-pressure area is a sample that, as in the aforementioned case, contains only a non-pressure area to produce and their reflected absorption with a UV-Vis spectrophotometer to eat.

Useful dyes which can be used in a coloring solution for the invention include basic dyes, acid dyes, direct dyes, disperse dyes and reactive dyes, which can be used singly or in combination. Among others, water-soluble basic and acid dyes are preferred. When two or more dyes are used in combination, the absorption wavelength of the dye having the largest reflected absorption becomes the maximum absorption wavelength of the dye Dyes selected.

helpful Basic dyes include "Crystal Violet "," Ethyl Violet "," Victoria Pure Blue "," Victoria Blue "," Methyl Violet "," Diabacis Magenta "(Mitsubishi Chemical Corporation), "Aizen Basic Cyanine 6GH "(Hodogaya Chemical Co., Ltd.), "Primocyanines BX Conc. "(Sumitomo Chemical Co., Ltd.), "Astrazon Blue G "(paint factories Bayer), "Diacryl Supra Brilliant 2B "(Mitsubishi Chemical Co., Ltd.), "Aizen Cathilon Turquoise Blue LH "(Hodogaya Chemical Co., Ltd.), "Aizen Diamond Green GH "(Hodogaya Chemical Co., Ltd.) and "Aizen Malachite Green "(Hodogaya Chemical Co., Ltd.).

helpful Acid dyes include "Acid Violet 5B "(Hodogaya Chemical Co., Ltd.), "Kiton Blue A "(CIBA)," Patent Blue AF "(BASF)," Rakuto Brilliant Blue FCF "(Rakuto Kagaku Kogyo Co., Ltd.), "Brilliant Aid Blue R "(Geigy)," Kayanol Canine 6B "(Nippon Kayaku Co., Ltd.), "Supranol Cyanine G "(paint factories Bayer), "Orient Soluble Blue OBB "(Oriento Kagaku Kogyo Co., Ltd.), "Acid Brilliant Blue 5G "(Chugai Kasei Co., Ltd.), "Acid Brilliant Blue FFR "(Chugai Kasei Co., Ltd.), "Acid Green GBH "(Takaoka Kagaku Kogyo Co., Ltd.) and "Acid Brilliant Milling Green B "(Hodogaya Chemical Co., Ltd.). (The trademarks mentioned in this application can be registered or not.)

Of the Content of these dyes in the dyeing solution used should be in the range of 0.01% by weight to 10% by weight, preferably in the range of 0.1% by weight to 5 wt .-%, lie.

helpful Solvent, in a dyeing solution for the invention can be used include water, alcohols, glycols, glycol monoalkyl ethers and glycol dialkyl ethers, which can be used individually or in combination. glycols, Glycol monoalkyl ethers and glycol dialkyl ethers can be used as processing solvents act, and therefore the development of a section in a Aftertreatment procedures are completed when part of the Silicone rubber layer can not be removed by development can and in the laser irradiated section after the development process remains.

Other Agents such as dyeing aids, organic acids, inorganic acids, Antifoams, plasticizers and detergents may, if necessary, be added.

The Temperature of a dyeing solution can be set in any case suitable, but is preferably in the range of 10 ° C up to 50 ° C. The development solution can as mentioned before Contain dyes to enable that development and dyeing of the print area are performed simultaneously.

Of the Printing area from which removes the ink repellent layer can be made by rubbing the plate surface with a piece of nonwoven composite, with cotton wool, a cloth or a sponge with such a dye solution or by pouring the staining solution over the Surface, followed by rubbing with a brush, colored become.

Such a method using a staining solution is advantageous because the desired Material can be selected from a wide range of available materials can, and a suitable contrast between the pressure and the non-pressure areas can be easily obtained without exception.

The Inventors led intensive studies regarding the factors that cause that conventional Printing plates not a big one Difference in reflected absorption as described above to reach. These studies showed that a major factor is the relationship between the absorption properties of the dye used for the dyeing and that of the material of the printing plate.

A Printing plate before dyeing or a precursor this should therefore be such that, if they are using the transmission method (1) the printing plate gives an ultraviolet absorption spectrum, which has a major peak in the range of 700 nm to 1200 nm, and (2) the ratio A / B between the absorbency at 830 nm (A) and that at 650 nm (B) not less than 3.0, preferably not less than 5.

One Printing plate precursor according to the invention is suitable for plate making with a semiconductor laser and therefore gives an absorption spectrum that is a major peak in the range from 700 nm to 1200 nm to the semiconductor laser beam to be sensitive in the near infrared range.

In order to simultaneously achieve easy plate verification and high image rendering capability, the ratio A / B between the absorbance at 830 nm (A) and that at 650 nm (B) in the Spek above a certain value.

The Reflection method and transmission method are for observation of the ultraviolet absorption spectrum. It is preferred the reflection method for a printing plate comprising a substrate of a non-UV transparent material As aluminum includes, use and the transmission method for one Pressure plate, which is a substrate made of a UV-transparent material such as polyethylene terephthalate.

By Achieving an absorption ratio (A / B) in the above-described range, it is possible to produce a printing plate the low absorption capacity in the range of visible light (400 nm to 700 nm), while a required sensitivity to semiconductor laser beams in the near Infrared range is maintained. By coloring such a printing plate with a dyeing method described above is it also possible to produce a printing plate in which the difference between the reflected absorption in the non-pressure area and that in the pressure range in the range described above, which is a further relief at disk verification.

So should for a printing plate before dyeing or a precursor of which the maximum absorbance in the ultraviolet absorption spectrum be in the range of 400 nm to 700 nm not more than 2.

Around to produce a directly recordable planographic printing plate, such As previously described UV absorption properties is preferred, a heat-sensitive Layer, the dyes, pigments, etc. with specific Contains absorption properties.

In the heat sensitive Layer of this invention has the surface in the laser-irradiated portion across from organic solvents an increased Solubility and an elevated one expansibility on what allows to remove the ink repellent layer by development, while the heat sensitive Layer remains.

dyes and pigments in the heat-sensitive Layer of the invention can be effectively used include dyes such as Cyanine dyes, polymethine dyes, phthalocyanine dyes and naphthalocyanine dyes and dyes and pigments such as dithiol metal complex compounds, Piazrenium compounds, squarilium compounds, croconium compounds, Azo compounds, bisazo compounds, Bisazostilbene compounds, naphthoquinone compounds, anthraquinone compounds, Perylene compounds, indoaniline compounds, benzothiopyran compounds, Spiropyran compounds, nigrosine compounds, thioindigo compounds, nitroso compounds, Quinoline compounds and fulgide compounds, these dyes and pigments (1) an ultraviolet absorption spectrum with the Main peak in the range of 700 nm to 1200 nm and (2) a relationship A / B between the absorbency at 830 nm (A) and the absorbance at 650 nm (B) in the spectrum over one certain level. Because this peak wavelength is often due to interactions between dyes / pigments and other components of the heat-sensitive Layer undergoes a shift, Printing plate samples should be prepared, and dyes and Pigments that meet the above conditions should be based on the results selected become.

Some such desirable Dyes are listed below.

in the Commercially available Dyes which are preferred include "KAYASORB" series CY-10, CY-17, CY-5, CY-4, CY-2, CY-20, CY-30 and IRG-002 (Nippon Kayaku Co., Ltd.); YKR-4010, YKR-3030, YKR-3070, YKR-2900, SIR-159, PA-1005, SIR-128, YKR-2080 and PA-1006 (Yamamoto Chemicals Inc.); "PROJET" 825LDI, "PROJET" 830NP, S174963 and S174270 (Avecia Limited); NK-2014, NK-2911, NK-2912, NK-4432, NK-4474, NK-4489, NK-4680, NK-4776, NK-5020, NK-5036 and NK-5042 (Hayashibara Seibutsukagaku Kenkyusho Co., Ltd.); IR2T and IR3T (Showa Denko K.K.); "EXCOLOR" 801K, IR-1, IR-2, TX-EX-801B and TX-EX-805K (Nippon Shokubai Co., Ltd.); CIR 1080 (Japan Carlit Co., Ltd.); IR98011, IR980301, IR980401, IR980402, IR980405, IR980406 and IR980504 (Yamada Chemical Co., Ltd.); "EPOLIGHT" V-149, V-129, V-63, III-184, III-192, IV-62B, IV-67, VI-19 and VI-148 (Epolin, Inc.).

Of the Content of such dyes should be in the range of 1 wt% to 40 Wt .-%, preferably from 5 wt .-% to 25 wt .-%, of the total ingredients the heat sensitive Layer lie. A content of not less than 1% by weight is preferable to allow efficient image reproduction, while dyes with a Content of not more than 40 wt .-% no negative effects on the properties of heat-sensitive Have layer.

A for the Invention to be used heat sensitive Layer should contain resins containing active hydrogen groups Main components included, as well as compounds containing such Resins, as an adjunct to such previously mentioned dyes.

Such Resins having active hydrogen groups include novolak resins and resole resins, produced by condensation reaction of such phenols as phenol, Cresol and xylenol with formaldehyde, as well as phenol-furfural resins, Furan resins, hydroxy-containing Urethane resins, p-hydroxystyrene copolymers, hydroxyethyl methacrylate copolymers, of which novolak resins are particularly preferred.

Such Compounds that interact with resins include blocked ones Isocyanate, epoxy-containing compounds, Acrylate compounds, metal chelate compounds, aldehyde compounds, mercaptohältige Compounds, alkoxysilyl compounds, amine compounds, carboxylic acid, vinyl-containing compounds, allyl containing compounds, Diazonium salt, azido compounds and hydrazine and leuco dyes and coumarin dyes, especially metal chelate compounds are preferred.

Such Metal chelate compounds include organic chelate compounds of Al, Ti, Mn, Fe, Co, Ni, Cu, Zn, Ge, In, Sn, Zr, Hf, etc., wherein preferred components are Ti, Zr, Hf, Sn and In. The ligands should preferably be pentanedionates.

preferred Metal chelate compounds include, but are not limited to, Aluminum bisethyl acetoacetate monoacetylacetonate, aluminum diacetylacetonatoethyl acetoacetate, Aluminum monoacetylacetonate bispropylacetacetate, aluminum monoacetylacetonatebisbutylacetacetate, Aluminum monoacetylacetonate bishexyl acetoacetate, aluminum monoethyl acetoacetate bispropyl acetoacetonate, Aluminum monoethyl acetoacetate bisbutyl acetoacetonate, aluminum monoethyl acetoacetate bishexyl acetoacetonate, Aluminum monoethyl acetoacetate bisnonyl acetoacetonate, aluminum dibutoxide monoacetacetate, Aluminum dipropoxide monoacetate acetate, aluminum butoxide monoethylacetate acetate, Aluminum s-butoxide bis (ethyl acetate), aluminum di-s-butoxide ethyl acetate, Aluminum 9-octadecenylacetate diisopropoxide, titanallyl acetoacetate triisopropoxide, Titanium di-n-butoxide (bis-2,4-pentanedionate), titanium diisopropoxide (bis-2,4-pentanedionate), Titanium diisopropoxide bis (tetramethylheptanedionate), titanium diisopropoxide bis (ethylacetate acetate), Titanium methacryloxyethyl acetoacetate triisopropoxide, titanium oxide bis (pentanedionate), Zirconium allylacetate triisopropoxide, zirconium di-n-butoxide (bis-2,4-pentanedionate), Zirconium diisopropoxide (bis-2,4-pentanedionate), zirconium diisopropoxide bis (tetramethylheptanedionate), Zirconium diisopropoxide bis (ethyl acetate), zirconium methacryloxyethyl acetoacetate triisopropoxide, Zirconium butoxide (acetylacetate) (bisethylacetacetate) and iron acetylacetonate.

These Resins and compounds with those present in the heat-sensitive layer Resins should be 20% to 95% by weight, preferably 30 wt .-% to 70 wt .-%, of the total solids content of the heat-sensitive Layer amount. A content of not less than 20% by weight serves to the occurrence of significant changes the solubility and the swelling rate as a result of changes in the heat-sensitive Layer, since this is involved in the image formation, to avoid. On the other hand, when the content is not more than 95% by weight, the maintain relative amount of infrared absorbing dyes, thereby preventing problems in the course of image formation.

Furthermore can be the heat sensitive Layer binder polymers, surface-active Containing agents and other various additives. The content of such Binder should be from 5% to 70%, preferably 10%, by weight to 50% by weight, of the total components of the heat-sensitive layer. One Content of not less than 5 wt% serves to deteriorate in terms of wear the plate and the coating properties of the color used to avoid while the ability for image reproduction is not reduced if the content is no longer is 70% by weight.

The thickness of the heat-sensitive layer in the form of a coated film should be 0.1 g / m ² to 10 g / m ² , preferably 1 g / m ² to 5 g / m ² , to ensure high plate wear of the printing plate, rapid evaporation of solvents and to ensure high productivity.

The permeability the heat sensitive Layer of the invention over Light with the same wavelength like the laser beam used for irradiation should not be less than 20%, preferably not less than 10%. A permeability of not less than 20% serves the total amount of light, by the heat sensitive Layer passes, reduce to effective reaction on the surface of the thermosensitive Ensure layer. Furthermore, a reduction of the total amount is used Light passing through the heat-sensitive Layer occurs, causing an excessive reaction in the heat-sensitive Layer through from under the heat-sensitive layer ago to avoid reflected energy. This facilitates the maintenance the heat sensitive Layer.

A of the characteristics of the printing plate of the present invention the use of an ink repellent layer. The usage an ink-repellent layer serves to problems such as differences in the pressure concentration due to non-uniform feed dampening water and negative environmental effects of alcohol constituents in humidification water, as these have a major impact on conventional water Can have printing process Use dampening water to remove ink repellent areas to build. Printing plates, which are an ink-repellent layer include, are particularly preferred for directly recordable planographic printing. The use of directly recordable planographic printing plates holds therein advantages that the control of the production of such plates on a computer, in contrast to conventional plate-making methods, in which the plate was exposed to light through a foil. It It is assumed herein that high quality prints are always by means of high reproducibility, and differences in the Pressure concentration due to non-uniform supply of dampening water can cause serious problems.

The The ink-repellent layer of the invention should be considered a good imaging ability, Printing ink-repellent properties and scratch resistance of silicone rubber be prepared. Either can Addition polymerized or condensation polymerized silicone rubber layers be used.

The Addition-polymerized silicone rubber layers may be polysiloxanes with carbon-carbon double bonds and SiH-containing polysiloxanes as well as reaction retarders for the control of hardening and curing include.

worin m für eine Ganzzahl von 2 oder mehr steht, und R¹ und R², die dieselben oder unterschiedlich voneinander sein können, jeweils für eine substituierte oder nichtsubstituierte Alkylgruppe mit 1–50 Kohlenstoffatomen, eine substituierte oder nichtsubstituierte Alkenylgruppe mit 2–50 Kohlenstoffatomen oder eine substituierte oder nichtsubstituierte Arylgruppe mit 4–50 Kohlenstoffatomen stehen.Preferred polysiloxanes having carbon-carbon double bonds include polysiloxanes containing vinyl groups, preferably polysiloxanes having vinyl groups at the molecular ends and / or in the main chain, more preferably polysiloxanes having vinyl groups at both molecular ends. Such compounds have a structure corresponding to the following general formula (I):

wherein m is an integer of 2 or more, and R ¹ and R ² , which may be the same or different, each represents a substituted or unsubstituted alkyl group having 1-50 carbon atoms, a substituted or unsubstituted alkenyl group having 2-50 carbon atoms, or a substituted or unsubstituted aryl group having 4-50 carbon atoms.

Not less than 50%, preferably not less than 80%, of all the groups denoted by R ¹ and R ² groups in formula (I) should be methyl in view of the ink repellency of the printing plate.

Vinyl-containing polysiloxanes with a molecular weight of several thousand to several hundred thousand can where those having a weight average molecular weight from 10,000 to 200,000, preferably 30,000 to 150,000, in terms of on handling properties, ink repellent plate properties and scratch resistance are preferred.

In particular, it should be measured by polystyrene-based weight-average molecular weight (Mw) by gel permeation chromatography, not less than 100,000, more preferably not less than 130,000.

Gel permeation chromatography (GPC) is a procedure for Liquid chromatography by means of which carried out a separation due to the different molecular size is the molecular weight distribution and the average molecular weight of polymers. If the sample solution is injected into a column, which filled with a certain gel is that has pores of a size the size of the volume, the a polymer chain in a diluted solution takes, similar is, penetrate molecules with a higher one Molecular weight, i. those with a larger molecular size in the solution, the gel slower from Pores on the surface and therefore move faster through the column and are eluted faster as molecules with a lower molecular weight. This tendency is used to create a GPC chromatogram, and the curve of the chromatogram is analyzed by a specific method to the molecular weight distribution or to determine the average molecular weight as required.

In the silicone rubber layer in a directly writable, anhydrous Planographic printing plates are polysiloxanes with carbon-carbon double bonds a very important factor that largely influences their characteristics can. High scratch resistance can be achieved if the weight average Molecular weight is not less than 100,000.

Furthermore should the ratio between the weight average molecular weight (Mw) and the number average Molecular weight (Mn) based on polystyrene, also by gel permeation chromatography measured, i. the variance Mw / Mn, not more than 7, preferably not more than 6. A variance (Mw / Mn) of not more as 7 serves to low molecular weight components too eliminate, resulting in an improvement of the properties of the silicone rubber layer and greatly increased Scratch resistance leads.

He follows the development and dyeing a directly recordable, water-free planographic printing plate by to brush in an automatic processor, proper brushing is the Silicone rubber layer comprising the non-printing area, necessary a good ability for imaging and good dyeing properties to achieve. As a silicone rubber layer with a high scratch resistance using a vinyl-containing Polysiloxane having a weight-average molecular weight of not produced less than 100,000 and a variance of not more than 7 which is an extremely practical Pressure plate provides little scratch in the silicone layer in non-pressure area, while a good ability for imaging and good dyeing properties to be kept.

The SiH-containing Polysiloxanes include compounds containing SiH groups in the molecular chain or at the molecular ends contain.

The Number of SiH groups in the SiH-containing Polysiloxane should not be less than 2 per molecule, preferably not less than 3 per molecule, be. The content of SiH-containing Polysiloxane should be 3 wt .-% to 20 wt .-%, preferably 5 wt .-% to 15% by weight of the total components of the silicone rubber layer be. With regard to the quantitative ratio with respect to polydimethylsiloxane should the molar ratio between SiH group and vinyl group in polydimethylsiloxane 1.5 to 30, preferably 10 to 20, amount. If the molar ratio is not less than 1.5, it is possible sufficient hardening to reach the silicone rubber layer while, unless the molar ratio is not is more than 30, it possible is to avoid that the rubber becomes so brittle that this is a negative Has an effect on the scratch resistance of the printing plate.

The reaction retardants include nitrogen-containing Compounds, phosphorus compounds and unsaturated alcohols. Especially Alcohols with acetylene groups are preferred. The content of the reaction retarder should 0.01 wt .-% to 10 wt .-%, preferably 1 wt .-% to 5 wt .-%, of total ingredients of the silicone rubber amount.

The curing catalysts include Group III transition metal compounds, preferably platinum compounds such as platinum, platinum chloride, chloroplatinic acid, olefin-coordinated platinum, alcohol-modified complexes of platinum and methylvinylpolysiloxane complexes of platinum. The content of such curing catalysts should be in the range of from 0.01% to 20%, preferably from 0.1% to 10%, by weight as a solid in the silicone rubber layer. When the content of the curing catalysts is not less than 0.01% by weight, the silicone rubber layer cures sufficiently and good adhesion with the heat-sensitive layer is achieved. On the other hand, when the content is not more than 20% by weight, the catalysis has not a negative effect on the pot life of the silicone rubber solution. The content of metals such as platinum in the entire components of the silicone rubber layer should be from 10 ppm to 1,000 ppm, preferably from 100 ppm to 500 ppm.

In addition to such components, the rubber may include: organopolysiloxane, Contains hydroxy groups, and silane / siloxane, the hydrolyzable functional groups which Components of condensation silicone rubber are; fillers such as silica to increase rubber strength; and silane coupling agents, Titanium adhesion promoter and aluminum adhesion promoter to increase liability. Such silane coupling agents include alkoxysilanes, Acetoxysilanes and ketoxime silanes, of which vinyl-containing silanes and ketoxime silanes are preferred.

ingredients of the condensation polymerized silicone rubber include hydroxy-containing polydimethylsiloxanes, Crosslinker (desacetate, deoxygenated, di-alcoholated, deaminated, desacetonated, deamidated, desaminoxylated, etc.) and curing catalysts.

The hydroxyhältigen Polydimethylsiloxanes can Hydroxy groups at the molecular ends and / or in the molecular chain wherein those having hydroxy groups at the ends of the molecule are preferred are. Their molecular weight should be from several thousand to several Hundreds of thousands are enough. In particular, their weight-average molecular weight should be in terms of the handling properties of such silanes and the ink-repellent properties and the scratch resistance thereof resulting plates 10,000 to 200,000, preferably 30,000 to 150,000.

The crosslinkers of condensation-polymerized silicone rubber layers include acetoxysilanes, alkoxysilanes, ketoxime silanes and allyloxysilanes expressed by the following formula (I): (R 1 ) 4 _ n SiXn (I) wherein n is an integer of 2 to 4, R ^{1 is} a substituted or unsubstituted alkyl, alkenyl or aryl group or a group consisting of two or more of them, and X is a halogen, a functional alkoxy , Acyloxyacyl, ketoximine, aminooxy, amide or alkenyloxy group. In the above formula, n representing the number of hydrolyzable groups should be 3 or 4.

Especially Preferred groups include methyltriacetoxysilanes, ethyltriacetoxysilanes, Vinyltriacetoxysilanes, vinyltri (methylethylketoximine) silanes and Tetra (methylethylketoximine) silanes.

Of the Content of the crosslinker shown in the general formula (I) should be 1.5% by weight to 20% by weight, preferably 3% by weight to 10% by weight, of the total components of the silicone rubber layer. Regarding the quantity ratio with respect to polydimethylsiloxane, the molar ratio of the functional group X to the hydroxy group in polydimethylsiloxane 1.5 to 10.0. is the molar ratio not less than 1.5, so dissolves the silicone rubber solution no gelation, and is it does not exceed 10.0, so these funds have no negative impact on the brittleness of the rubber or the scratch resistance of the resulting printing plates.

The curing include acids, Bases, amines, metal alkoxide, Metalldiketenat and metal salts organic acids, of which metal salts of organic acids, wherein the metal tin, lead, zinc, iron, cobalt, calcium or manganese is, are preferred. Such compounds include dibutyltin diacetate, Dibutyltin dioctate and dibutyltin dilaurate. The content of such curing catalysts should be 0.01 wt% to 20 wt%, preferably 0.1 wt% to 10 Wt .-%, as a solid in the silicone rubber layer amount. Is the salary the added catalysts not less than 0.01 wt .-%, so the silicone rubber is sufficiently cured, and good adhesion with the heat sensitive Layer is reached. is On the other hand, the content is not more than 20% by weight, so catalysis has no negative effect on the pot life of the silicone rubber solution.

The thickness of such a silicone rubber layer should be 0.5 g / m ² to 20 g / m ² , preferably 1 g / m ² to 4 g / m ² . If the thickness of the layer is not less than 0.5 g / m ² , ink repellency, scratch resistance and pressure deterioration develop permanently in the resulting printing plate, while maintaining a good developing property and good ink consumption at a thickness of not more than 20 g / m ² ,

Plate-like substrates with high dimensional stability are used for directly recordable lithographic printing plates embodying the present invention are used. Such plate-like materials having high dimensional stability include paper; Metals such as stainless steel and aluminum; Plastics such as polyester, polyethylene and polypropylene; and metal-laminated or metal-coated paper or plastic sheets (the metal being aluminum, etc.). Of these materials, aluminum plates are particularly preferred since they have high dimensional stability and are inexpensive. Polyethylene terephthalate film is also preferred as the plate material for small offset printing. If the absorbency of a transparent substrate is to be determined, the printing plate is placed on white paper and measured by a densitometer from above.

One Directly writable planographic printing plate precursor of the invention should preferably a thermally insulating Layer, to avoid that of the laser beam used Outgoing heat is released by the substrate. A primer layer, the usual is used to increase the adhesion between the substrate and the ink-accepting Layer (heat-sensitive Layer) can be used for this purpose.

Becomes a thermally insulating Layer in directly writable planographic printing plate precursor of When using the invention, such an insulating layer should be as follows Meet requirements: Adhesion between the aluminum substrate and the ink-accepting Layer (heat-sensitive Layer), which for a longer one Time sufficiently strong and stable and highly resistant to the for development and pressure used solvents is.

Materials, that meet these conditions, include epoxy resin, polyurethane resin, phenolic resin, acrylic resin, alkyd resin, Polyester resin, polyamide resin, urea resin, polyvinyl resin, polyvinyl butyral resin, Casein -containing Material and gelatin-containing Material, of which polyurethane resin, polyester resin, acrylic resin, epoxy resin and urea resin are preferred, alone or in combination can be used.

The thickness of such a heat-insulating layer in the form of a coated film should be 0.5 g / m ² to 50 g / m ² , preferably 1 g / m ² to 10 g / m ² . If it is not less than 0.5 g / m ² , the layer can prevent the formation of morphological defects on the substrate surface and protect the substrate from adverse chemical effects. A heat-insulating layer having a thickness of not more than 50 g / m ² is economically advantageous.

One directly recordable planographic printing plate precursor of the invention can be used with Protective film laminated or covered with a protective layer, to protect the ink repellent layer. Preferred film materials include polyester, polypropylene, polyvinyl alcohol, saponified copolymer of ethylene and vinyl acetate and polyvinylidene chloride.

The Manufacturing process for Directly recordable planographic printing plate precursors according to the invention may, like follows become: a conventional Coater like an opposite one Roll coater, an air knife coater, gravure coater, Dye coater or Meyer coater or a coater The rotation type like an axis machine is used to do that Substrate having a composition for a heat-insulating layer depending on Need to coat, then for a few minutes at 100 ° C up to 300 ° C is heated or irradiated with active light for curing, after which applying a composition for the ink receiving layer and heating / drying at 50 ° C up to 180 ° C a few tenths of a second to a few minutes, as needed, done to the curing sure.

Subsequently, will a silicone rubber composition is applied and at 50 to 200 ° C a few minutes long heat treated, to prepare a silicone rubber layer. Then it will be on the Layer laminated a protective film, or it is coated with a protective layer, if necessary, covered.

The Manufacturing process for The directly recordable planographic printing plate of the invention is below described in more detail.

The Manufacturing process for a directly recordable planographic printing plate according to the invention may be a method for converting the heat-sensitive Layer with laser beam irradiation directly after peeling off Protective film or through the protective film and another method for removing the ink repellent layer by brushing in Presence of water while the laser-irradiated, heat-sensitive layer remains intact.

One Laser in the wavelength range from 300 nm to 1500 nm can for the laser beam irradiation can be used. The use of a Semiconductor laser or a YAG laser in the near infrared range is illuminated in terms of handling the plate material in a Space preferred. In particular, a laser with a wavelength of 780 nm, 830 nm or 1064 nm is preferred.

Becomes he is irradiated with a laser beam, so absorbs the infrared-absorbing Dye in the heat-sensitive Layer the laser beam and thereby generates heat. Is the permeability the heat sensitive Layer low, so the laser beam is very close to the surface of the heat-sensitive layer absorbed, resulting in higher Temperatures nearby the surface the heat-sensitive layer leads.

Thus, by controlling the dose of the laser beam, the reaction to portions near the surface of the heat-sensitive layer can be restricted. The dose of the laser beam is preferably in the range of 100 mJ / cm ² to 500 mJ / cm ² .

After this he was irradiated with the laser beam, the printing plate precursor with an organic solvent, if necessary, be treated to the surface of the heat-sensitive layer dissolve or swelling, after which the precursor in the presence of water brushed is to ensure development.

The organic solvent used before should be a glycol compound or a glycol ether compound represented by the following general formula (II): R 3 O- (CHR 2 -CH 2 -O-) n R 4 (II) wherein R ^{2 represents} a hydrogen atom or an alkyl group having 1-5 carbon atoms, R ³ and R ^{4 represents} a hydrogen atom or an alkyl group having 1-15 carbon atoms, and n denotes an integer of 1 to 12.

Links, which are particularly preferred include diethylene glycol, triethylene glycol, Tetraethylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, Polyoxypropylene glycol (Mw: 200), polyoxypropylene glycol monobutyl ether (Mw: 1,200), tetraethylene glycol mono-2-ethylhexyl ether and diethylene glycol mono-2-ethylhexyl ether.

Such Processing solvent, as they were previously listed, should be alkaline compounds or Amine compounds include. Preferred compounds include diethylene glycolamine, N- (β-aminoethyl) aminoethanol, Diethanolamine, N-methyldiethanolamine, Morpholine, N-methylmorpholine and N- (3-aminopropyl) morpholine. The content of this Amine compounds in such processing solvents may be 0.1 wt% to 30 wt .-%, preferably 0.5 wt .-% to 20 wt .-%, be.

Furthermore, can such processing solvents Water, alcohols, carboxylic acids and detergents, if necessary.

Such Processing solvent serve to heat sensitive Dissolve layer in the laser-irradiated section or swell, wherein however, the temperature of the processing solvent kept constant should be to ensure permanent dissolving and swelling. Depending on the processing time, in terms of easy stabilization the temperature is the optimum temperature in the range of 10 ° C to 50 ° C, preferably from 35 ° C up to 45 ° C, lie.

The Development process can be done manually but should preferably be by an automatic developing machine for anhydrous planographic printing plates such as TWL-1160, TWL-650 and TWL-860 from Toray Industries, Inc. or by other means disclosed in Japanese Patent No. 2,864,907, Japanese Patent Publication JP-A-hei-6-258,842, Japanese Patent Publication JP-A-hei-6-258,843, Japanese Patent Publication JP-A-hei-6-258844 and Japanese Patent Publication JP-A-hei-7-92,692.

For brushing, a typical brush consists of arrays of brush bristles having a diameter of 20 μm to 500 μm, which are fixed in grooves provided on a metal or plastic body. A brush may consist of bristles which are fixed in radial directions on the metal or plastic body, or of bristles which are fixed on a plastic sheet or piece of fabric, then wrapped around a metal or plastic body.

A to be used brush Preferably, bristles should be made of at least one of the following materials chosen Comprising: polyvinyl chloride, polyamide, polyethylene terephthalate, Polybutylene terephthalate and polypropylene. Such a brush hurt the ink-repellent layer on the pressure plate is not and is able to apply sufficient force to the ink repellent Completely remove the layer from the laser-irradiated section.

The Number of revolutions of the brush roller used should be in the range from 10 rpm to 1,000 rpm, preferably 200 rpm to 600 rpm, lie. The ink repellent layer in the laser irradiated section Can be removed more efficiently when the brush roll while of rotating in the axial direction reciprocated. To the whole Removal of the ink-repellent layer from the laser-irradiated Section, it is important to provide multiple brush rolls, some of them in the same direction as the transported printing plate rotate while rotate the others in the opposite direction.

Instead of such development systems described above, the laser irradiation, Treatment with organic solvents and brushes in the presence of water, a "water development system" is also preferred by the treatment with organic solvents not done is, but the laser-irradiated printing plate only by brushing in Presence of water is being developed.

A directly writable planographic printing plate is made by staining with completed a dye as described above.

The Silicone rubber layer in non-pressure area may be over long Easily replace time, though the processing solvent or the staining solution in the dyed Restrained plate become. Thus, a method for rinsing can be provided around this processing solvent or this staining solution completely from to remove the plate. The temperature of the rinse water can be for everyone However, if appropriate, it is preferably within the range of 10 ° C up to 50 ° C.

preferred embodiments of the invention are described below with reference to the following examples, Comparative examples and reference examples described in more detail, wherein the Reference examples for explanation mentioned the invention However, methods are described which are within the scope of the invention fall because the ultraviolet spectrum is not transmitted by the transmission method can be measured.

[Reference Example 1]

A solution having the composition described below was applied to a degreased aluminum plate having a thickness of 0.24 mm, which was then dried at 200 ° C for 2 minutes to form a heat-insulating layer of 3 g / m ² .

<Composition of the heat-insulating Layer (solids content: 19.6 parts by weight)>

(1) Epoxy phenolic resin ("Kancoat" 90T-25-3094, Kansai Paint Co., Ltd.): 15 parts by weight

[Composition of the solvent]

(1) Dimethylformamide: 85 parts by weight

Over the heat-insulating layer, a heat-sensitive layer described below was formed to a dry film thickness of 1.0 g / m ² . Heat treatment was carried out at 140 ° C for 1 minute.

<Heat-sensitive Layer 1>

• (1) (3-Butyl-1,1-dimethyl-2- [2 [2-diphenylamino-3 - [(3-butyl-1,3-dihydro-1,1-dimethyl-2H-benzindol-2-ylidene ) ethylidene] -1-cyclopenten-1-yl] ethynyl] -1H-benzindoliumperchlorat): 15 parts by weight
• (2) Ferric acetylacetonate (Nakarai Chemical, Ltd.): 10 parts by weight
• (3) resole resin ("Sumirac" PC-1, Sumitomo Durez Co., Ltd.): 75 parts by weight
• (4) Tetrahydrofuran: 100 parts by weight
• (5) Dimethylformamide: 100 parts by weight
• (6) Methyl ethyl ketone: 700 parts by weight

Subsequently, a silicone rubber layer described below was formed to a dry film thickness of 2.0 g / m ² . Dry (wet heat drying) was carried out at 120 ° C for 1 minute.

<Silicone rubber layer 1>

• (1) polydimethylsiloxane (molecular weight about 50,000, hydroxy at both ends): 100 parts by weight
• (2) (Methyl ethyl ketone oxime) silane (vinyl tris): 8 parts by weight
• (3) Dibutyltin diacetate: 0.5 part by weight
• (4) 3-aminopropyltriethoxysilane: 0.5 part by weight
• (5) Isoparaffin-based hydrocarbon ("Isopar" E, Exxon Chemical Japan LTD): 1,400 parts by weight

A multilayer plate was coated with a protective film (polypropylene, 8 μm thick) laminated with a calender roll to form a directly writable, produce anhydrous planographic printing plate precursor.

This planographic printing plate precursor was fixed on a plate making machine (FX400-AP, Toray Engineering Co., Ltd.) and with semiconductor laser beam (wavelength 830 nm, beam diameter 20 μm) under the conditions of an irradiation time of 10 μs and an irradiation energy of 125 mJ / cm ² irradiated.

Subsequently was the plate in pretreatment solution (NP-1, Toray Industries, Inc.) for Anhydrous planographic printing plates of negative type immersed for 1 minute and by brushing with one piece Gauze ("Haize Gauze", Asahi Kasei Corporation) developed, resulting in the formation of an anhydrous planographic printing plate led from the negative type, the silicone rubber layer only in the laser-irradiated section had lost. Subsequently, dyeing was carried out by brushing for one minute Plate in nitrogen atmosphere at 25 ° C with a piece of Haize Gauze, which is a dyeing solution of contained below composition.

<Dyeing solution>

• (1) Ethylcarbitol: 10 parts by weight
• (2) Water: 89.5 parts by weight
• (3) Crystal Violet (absorption maximum at 592 nm): 0.5 parts by weight

After this she was rinsed in water for a minute, the obtained colored Plate of absorbance measurement at 592 nm with a UV-Vis spectrophotometer (U-3210, Hitachi, Ltd.) equipped with an integration sphere was, subjected. The absorbency of the non-pressure area was 0.8 while the absorption capacity the pressure range was 1.5, which is an absorption difference of 0.7 results. The pressure and non-pressure areas were easily penetrated distinguished optical viewing.

Comparative Example 1

A heat-sensitive layer having the composition described below was applied to the heat-insulating layer prepared in Example 1. The dry film thickness was 1.0 g / m ² , and the heat treatment was carried out at 140 ° C for one minute.

<Heat-sensitive Layer 2>

• (1) Polymethine compound ("IRT", Showa Denko K.K.): 15 parts by weight
• (2) Ferric acetylacetonate (Nakarai Chemical, Ltd.): 10 parts by weight
• (3) "Sumirac" PC 1 (resole resin, Sumitomo Durez Co., Ltd.): 75 parts by weight
• (4) Tetrahydrofuran: 100 parts by weight
• (5) Dimethylformamide: 100 parts by weight
• (6) Methyl ethyl ketone: 700 parts by weight

A Silicone rubber layer was as described in Example 1 on formed of the plate, which is then coated with the protective film (polypropylene film, 8 μm thick) laminated using a calender roll to one directly recordable, waterless planographic printing plate precursor too form.

A colored Printing plate was made by the same method as in Reference Example 1 produced. Their absorption capacity was by means of the same Method as measured in Reference Example 1, resulting in that the absorption capacity of the non-printing area was 1.3, while the absorbency of the printing area 1.5 was. Thus, the difference in absorbency was 0.2. The pressure and non-pressure areas could be visualized not easily distinguished from each other.

[Reference Example 2]

«Making a direct recordable planographic printing plate precursor »

A solution having the composition described below was applied to a degreased aluminum plate having a thickness of 0.24 mm (Kobe Steel, Ltd.), after which it was dried at 150 ° C for 80 seconds to obtain a heat-sensitive layer having a thickness of 1 To form 5 g / m ² .

<Heat-sensitive Layer 3>

• (a) ("Projet" 825LDI, Avecia Limited): 11 parts by weight
• (b) acetylacetone solution titanium di-n-butoxide (bis-2,4-pentanedionate) ("Nasem Titan", Nippon Chemical Industrial Co., Ltd.): 9 parts by weight (solid content for calculation assumed to be 40% by weight. 9 parts by weight as a solid)
• (c) phenolic novolac resin ("Sumi-light Resin "PR50622, Sumitomo Durez Co., Ltd.): 60 parts by weight
• (d) polyurethane ("Sanpren" T1331 D, Sanyo Chemical Industries, Ltd.): 10 parts by weight (10 parts by weight as a solid)
• (e) m-xylylenediamine / glycidyl methacrylate / 3-glycidoxypropyltrimethoxysilane 1/3/1 in molar ratio, Addition product: 10 parts by weight
• (f) tetrahydrofuran: 700 parts by weight
• (g) Dimethylformamide: 100 parts by weight
• (h) Ethanol: 100 parts by weight

thereupon was a silicone rubber layer having the below-described Composition with a slot dye coater up to applied to a dry film thickness of 2.0 microns and at 125 ° C for 2 minutes dried to produce a directly recordable planographic printing plate precursor 3.

<Silicone rubber layer 2>

• (a) α, ω-divinylpolydimethylsiloxane (Molecular weight: about 60,000): 100 parts by weight
• (b) (methylhydrogensiloxane) - (dimethylsiloxane) copolymer with Methyl at both ends (HMS-501, Chisso Corporation, Number of SiH groups per molecular weight 0.69 mol / g): 7 parts by weight
• (c) Vinyl tri (methyl ethyl ketoxime) silane: 3 parts by weight
• (d) Platinum Catalyst (SRX-212, Dow Corning Toray Silicone Co., Ltd.): 5 parts by weight
• (e) "Isopar" E (Exxon Chemical Japan Ltd.): 1,000 parts by weight

«Making a direct recordable planographic printing plate »

The directly recordable planographic printing plate precursor previously prepared was fixed on a GX-3600 plate making machine manufactured by Toray Industries, Inc. and irradiated with a semiconductor laser having a wavelength of 830 nm (irradiation dose 175 mJ / cm ² , 2,400 dots per inch ( ie per 2.54 cm), 175 lines per inch (ie per 2.54 cm)).

Subsequently was the directly recordable planographic printing plate using a automatic processor for planographic printing plates from Toray Industries, Inc., TWL-860KII, the first, second and third containers Processing solvent 1, as described below, water or processing solvent 2, as described below. Treatment with processing solvent 1 and processing solvent 2 was at 40 ° C for 30 seconds or 15 seconds at 25 ° C carried out. The treatment with water in the second container was for 15 seconds at 25 ° C.

in the first container was the processing solvent on the Pressure plate poured to dissolve the surface of the heat-sensitive layer or swell.

<Processing solvent 1>

• (a) Diethylene glycol: 80 parts by weight
• (b) Diethylene glycolamine: 15 parts by weight
• (c) 2-Ethylhexyl sodium sulfate (anionic detergent, 40% aqueous Solution): 1 part by weight
• (d) water: 4 parts by weight

<Processing solvent 2>

• (a) Butyl carbitol: 20 parts by weight
• (b) 2-ethylhexanoic acid: 1 part by weight
• (c) 2-ethylhexylsodium sulfate (anionic detergent): 0.5 part by weight
• (d) Dye (C.I. Basic Blue 7 CI42594): 0.02 parts by weight
• (e) Dye (C.I. Basic Blue 1 CI42095: maximum absorbency at 599 nm): 0.08 parts by weight
• (f) Water: 78.4 parts by weight

The Processing solvent was removed from the printing plate at the time when the Plate was automatically transported from the first container in the second container. In the second tank, the pressure plate was rubbed off with a brush, in the same direction as the conveying direction of the printing plate rotated while rinsed with water has been. In the third container was the plate with a brush rubbed, which rotated in the opposite direction.

The previously described method led to form a directly writable planographic printing plate, which is their Silicone rubber layer had lost while being the heat-sensitive Layer in the laser irradiated section maintained. As in reference example 1 became the absorbency measured at 599 nm of the printing plate, showing the result that the absorption capacity of the non-printing area was 0.7 while the absorbency of the Pressure range was 1.3, resulting in a difference in terms of the absorption capacity of 0.6.

«Evaluation of simplicity the disk check 1 »

The Ease of disk verification was based on observation of the resulting printing plate with a magnifying glass with 25x magnification rated. Halftone dots the size of 1 % were clearly seen, indicating that the disk check especially was easy to accomplish.

«Assessment of the ability for imaging »

The The resulting printing plate was transferred to a 25-sheet fed offset press "Sprint" from Komori Corporation fixed and for printing on uncoated paper (62.5 kg / kiku [636 × 939 mm]) with "Dry-O-Color" cyan anhydrous Planographic printing ink used by Dainippon Ink and Chemicals Inc. The prints were observed to determine the imaging ability and a high ability to Imaging of 1 to 99% has been confirmed.

«Evaluation of the Impact the disk check 2 »

The previously for the printing plate used was taken off the press, and the printing plate with the ink not removed was with a magnifying glass with 25x magnification considered to the ease of disk verification too determine. Halftone dots with a size of 1% were clearly visible what to conclude leaves, that the disk check especially was easy.

«Observation of the UV spectrum the printing plate »

The UV spectrum of the previously described direct write planographic printing plate precursor has been by the reflection method with the U-3210 spectrophotometer from Hitachi, Ltd., observed with an integration sphere.

Of the Main peak was detected at 750 nm, and the absorbency at 830 nm (A) and that at 650 nm (B) were 1.34 and 0.72, respectively their relationship (A / B) amounted to 1.86.

The maximum absorbance in the range of 400 to 700 nm was 1.99, confirming that the maximum was less than 2.

Comparative Example 2

«Making a direct recordable planographic printing plate precursor »

One Printing plate precursor was prepared by the same method as in Reference Example 2, with the exception that the heat sensitive Layer had the composition described below.

<Heat-sensitive Layer 4>

• (a) ("Kayasorb" PS101, Nippon Kayaku Co. Ltd.): 11 parts by weight
• (b) acetylacetone solution of titanium di-n-butoxide (bis-2,4-pentanedionate) ("Nasem Titan", Nippon Chemical Industrial Co., Ltd.): 9 parts by weight (solid content for calculation assumed to be 40% by weight. 9 parts by weight as a solid)
• (c) phenolic novolac resin ("Sumi-light Resin "PR50622, Sumitomo Durez Co., Ltd.): 60 parts by weight
• (d) polyurethane ("Sanpren" T1331 D, Sanyo Chemical Industries, Ltd.): 10 parts by weight (as 10 parts by weight of solids)
• (e) m-xylylenediamine / glycidyl methacrylate / 3-glycidoxypropyltrimethoxysilane 1/3/1 in molar ratio, Addition product: 10 parts by weight
• (f) tetrahydrofuran: 800 parts by weight
• (g) Dimethylformamide: 100 parts by weight

The Evaluation was carried out as in Reference Example 2. For the received Prints became a good skill for imaging 1-99 % approved, however, for the pressure plate only half-tone points down to 4% were confirmed. In the case of the ink-retaining printing plate, only halftone dots were used down to 3% confirmed.

The Observation of the UV spectrum showed that the main peak at 810 nm, with the absorbance at 830 nm (A) and that at 650 nm (B) were 1.76 and 1.62, respectively, and their ratio (A / B) to 1.09, i. to a value of less than 1.5.

The absorbance at 599 nm of the printing plate was measured as in Reference Example 1, which indicated that the absorbency of the non-pressure area 1.6, while that of the printing area was 1.7, giving a difference of 0.1. The ease of disk verification was as assessed in Reference Example 2, but it was difficult to distinguish the pressure range from the non-pressure range.

[Example 1]

«Making a direct recordable planographic printing plate precursor »

A solution having the composition described below was applied by a coater to a 50 μm thick polyethylene terephthalate film ("Lumirror" T150, Toray Industries, Inc.) and dried at 150 ° C for 80 seconds to obtain a heat-sensitive layer of 1.5 g / m². m ² produce.

<Heat-sensitive Layer 5>

• (a) (IR2T, Showa Denko K.K.): 11 parts by weight
• (b) acetylacetone solution of titanium di-n-butoxide (bis-2,4-pentanedionate) ("Nasem Titan", Nippon Chemical Industrial Co., Ltd.): 9 parts by weight (solid content for calculation assumed to be 40% by weight. 9 parts by weight as solids)
• (c) phenolic novolac resin ("Sumi-light Resin "PR50622, Sumitomo Durez Co., Ltd.): 60 parts by weight
• (d) polyurethane ("Sanpren" T1331 D, Sanyo Chemical Industries, Ltd.): 10 parts by weight (as 10 parts by weight of solids)
• (e) m-xylylenediamine / glycidyl methacrylate / 3-glycidoxypropyltrimethoxysilane 1/3/1 in molar ratio, Addition product: 10 parts by weight
• (f) tetrahydrofuran: 800 parts by weight
• (g) Dimethylformamide: 100 parts by weight

Subsequently was a silicone rubber layer having the composition described below with a pre-coating machine up to a dry film thickness of 2.0 μm applied and dried for 2 minutes at 125 ° C to a direct recordable planographic printing plate precursor.

<Silicone rubber layer 1>

• (a) α, ω-divinylpolydimethylsiloxane (Molecular weight: about 60,000): 100 parts by weight
• (b) (methylhydrogensiloxane) - (dimethylsiloxane) copolymer with Methyl at both ends (HMS-501, Chisso Corporation, Number of SiH groups per molecular weight 0.69 mol / g): 7 parts by weight
• (c) Vinyl tri (methyl ethyl ketoxime) silane: 3 parts by weight
• (d) Platinum Catalyst (SRX-212, Dow Corning Toray Silicone Co., Ltd.): 5 parts by weight
• (e) "Isopar" E (Exxon Chemical Japan Ltd.): 1,000 parts by weight

Of the directly recordable planographic printing plate precursor prepared previously was irradiated with a laser beam as in Reference Example 2, fixed to a 0.15 mm thick aluminum plate and as in Reference Example 2 designed to form a directly writable planographic printing plate.

The Evaluation was made as in Reference Example 2. The ability for imaging for Prints was 1-99%, and the ease of disk verification for that The printed and inked plate prepared was in both cases not less than 1%. Accordingly, good results were achieved. The absorbance of 599 nm of the printing plate was measured, indicating that the absorption capacity of the Non-pressure range was 0.3 while that of the pressure range was 1.2, resulting in a difference in absorbance of 0.9. The pressure range and the non-pressure range could be easily distinguished.

«Observation of the UV spectrum of the printing plate precursor »

The UV spectrum of the directly recordable planographic printing plate precursor, the previously described was by means of the transmission method observed.

Of the Main peak was detected at 858 nm, and the ratio A / B between the absorption capacity at 830 nm (A) and that at 650 nm (B) was 12.6. The maximum absorbance in the range of 400 to 700 nm was 0.31, which confirmed that the maximum was less than 2.

Comparative Example 3

One Printing plate precursor was prepared by the same method as in Example 1, with except that "Kayasorb" IR820 (B) (Nippon Kayaku Co., Ltd.) is used as component (a) of the heat-sensitive layer has been.

The Evaluation was carried out as in Example 1. For the prints obtained was a good ability for imaging 1-99 % approved, however, for the pressure plate only half-tone points down to 4% were confirmed. For the Printing inked printing plates were only down to half tone dots up to 3% confirmed. The absorbency at 599 nm of the printing plate was measured as in Reference Example 1. The absorbance of the printing area and that of the non-printing area was 1.2 and 1.4, which gave a difference in absorbance of 0.2. It was impossible to Differentiate pressure range from non-pressure range.

The UV spectrum was observed by the transmission method. Of the Main peak was observed at 838 nm, and the ratio A / B between the absorption capacity at 830 nm (A) and that at 650 nm (B) was 2.48, i. it amounted to a value below 3.0. The maximum absorption capacity in the range from 400 nm to 700 nm was 1.29, which confirms that the maximum is less than 2 was.

[Reference Example 3]

One Direct writable planographic printing plate precursor was made by the same method as prepared in Reference Example 2, except that component (a) the heat-sensitive Layer was as shown in Table 1, followed by laser irradiation and development as in Reference Example 2.

The absorption properties were measured by the reflection method. The main peak was at 810 nm, and the ratio A / B between the absorbance at 830 nm (A) and that at 650 nm (B) was 4.11, that is, above 1.5. The maximum absorbance in the range of 400 nm to 700 nm was 0.31, confirming that the maximum was less than 2. The absorbance at 599 nm of this printing plate was measured as in Reference Example 1. The absorbency of the non-pressure area and that of the pressure area was 1.0 and 1.4, respectively, with a difference in absorbance of 0.4.

Quality Results were for the ability for imaging, ease of panel verification, and ease of reviewing one Obtained ink containing plate (Table 2).

Table 1

Table 2

(Dye 17)

[Examples 2-6]

One Direct writable planographic printing plate precursor was made by the same method as prepared in Example 1, except that component (a) the heat-sensitive Layer was as shown in Table 3, followed by laser irradiation and development as in Example 1.

In In each of the examples, the absorption properties were determined by the Transmission method measured. The ratio A / B between the absorbance at 830 nm (A) and that at 650 nm (B) was above 3.0. The maximum absorption capacity in the range from 400 nm to 700 nm was less than 2.

Good results were obtained for the imaging ability, the ease of panel verification and obtained the ease of checking the ink-containing plate (Table 4). The absorbance at 599 nm of the printing plate was measured as in Reference Example 1. The difference in absorbency between the non-pressure area and the pressure area was over 0.3 in all examples (Table 5).

Table 3

Table 4

Table 5

(Dye 9)

[Reference Example 4]

<Production of a directly writable Planographic printing plate precursor>

A solution having the composition described below was applied to a degreased aluminum plate having a thickness of 0.24 mm (Kobe Steel, Ltd.), followed by drying at 150 ° C for 80 seconds to obtain a heat-sensitive layer having a thickness of 1, 5 g / m ² to form.

<Heat-sensitive Layer>

• (a) (YKR-2900, Yamamoto Chemicals Inc.): 11 parts by weight
• (b) acetylacetone solution of titanium di-n-butoxide (bis-2,4-pentanedionate) (AKT853, Gelest Inc.): 9 parts by weight (solids content for calculation with 40% by weight) accepted. 9 parts by weight as a solid)
• (c) phenolic novolac resin ("Sumi-light Resin "PR50622, Sumitomo Durez Co., Ltd.): 60 parts by weight
• (d) Polyurethane ("Sanpren" T1331D, Sanyo Chemical Industries, Ltd.): 10 parts by weight (as 10 parts by weight of solids)
• (e) m-xylylenediamine / glycidyl methacrylate / 3-glycidoxypropyltrimethoxysilane 1/3/1 in molar ratio, Addition product: 10 parts by weight
• (f) tetrahydrofuran: 800 parts by weight
• (g) Dimethylformamide: 100 parts by weight

Subsequently was a silicone rubber layer having the composition described below with a slot dye coater until dry Foil thickness of 2.0 μm applied and dried for 2 minutes at 125 ° C to a direct recordable planographic printing plate precursor.

<Silicone rubber layer>

• (a) α, ω-divinylpolydimethylsiloxane 1 (weight average molecular weight (Mw): 131,000, variance (Mw / Mn): 5.24): 100 parts by weight
• (b) (methylhydrogensiloxane) - (dimethylsiloxane) copolymer with Methyl at both ends (HMS-151, Gelest Inc., MeSiH 15-18 mol%): 4 parts by weight
• (c) Vinyl tri (methyl ethyl ketoxime) silane: 3 parts by weight
• (d) Platinum Catalyst (SRX-212, Dow Corning Toray Silicone Co., Ltd.): 5 parts by weight
• (e) ("Isopar" E, Exxon Chemical Japan Ltd.): 1,035 parts by weight

Laser irradiation, Development and evaluation were performed as in Reference Example 2. Both for the prints as well as for The printing plates has a good imaging ability for 1-99% of the Halftone dots confirmed. The absorption capacity at 599 nm of the printing plate was measured as in Reference Example 1. The absorbency of the pressure area and that of the non-pressure area was 0.4 or 1,3, with a difference in the absorbency of 0.9.

Subsequently was the silicone rubber layer in the non-pressure area with "Isopar" E swelled and observed. There were no material errors, which may be due to to brush in the automatic developing machine could arise.

The UV spectrum was observed. The main peak was determined at 810 nm, and the absorbency at 830 nm and that at 650 nm were 1.67 and 0.41, respectively A / B ratio of 4.11, i. a value over 1.5.

[Measurement of molecular weight distribution by gel permeation chromatography]

GPC measurement the molecular weight distribution of vinyl polydimethylsiloxane became performed under the following conditions.

Equipment: Gel Permeation Chromatograph (GPC-224, Waters) (LS1) Data Processing: GPC Data Processing System (Toray Research Center, Inc.) Column: TSK Gel GMH × 1 (Inner Diameter 7.8 mm, Length 30 cm ) (2 columns used), (Tosoh Corporation)
Solvent: toluene
Flow rate: 1.0 ml / min
Sample: Concentration - 0.3%
Solubility - 100%
Filter - My Shori Disk H-13-5
Injected volume: 200 μl
Detector: Differential Refractometer (401, Waters)
Molecular Weight Calibration: 10 Monodisperse Polystyrene Products (Tosoh Corporation) 1. F-288-01 Molecular Weight (M) 2890000 2. F-80-0 706000 3. F-40-01 355000 4. F-20-01 190000 5. F-10-01 96,400 6. F-4-01 37,900 7. F-2-01 18,100 8. A-5000-01 5970 9. A-2500-01 2630 10. A-500-01 500

commercial applicability

The The present invention provides directly recordable planographic printing plates ready, which is a very good ability for imaging and easy to check.

Claims (12)

A process for producing a direct-write planographic printing plate, comprising: irradiating a directly recordable planographic printing plate precursor comprising at least a substrate, a heat-sensitive layer, and an ink-repellent layer in this order with a laser beam, removing the ink-repellent layer from the laser-irradiated portion, and coloring the lithographic printing plate A printing area free of this ink repellent layer with a coloring solution wherein the difference between the reflected absorption of the non-printing area having the ink repellent layer and the reflected absorption of the printing area observed after the dyeing the printing plate at the maximum absorption wavelength of the dye in the dyeing solution is not less than 0.3 and not more than 2.0, and wherein the directly recordable planographic printing plate precursor has an ultraviolet absorption spectrum which is examined by the transmission method, having the following characteristics: (1 ), the major peak of the ultraviolet absorption spectrum is between 700 nm and 1200 nm, and (2) the A: B ratio between the absorbance at 830 nm (A) and the absorbance at 650 nm (B) is not less than 3.0. The method of claim 1, wherein the maximum absorption wavelength of the Dye in the range of 500 nm to 650 nm. The method of claim 1 or 2, wherein the maximum absorbance of the directly writable planographic printing plate precursor in the wavelength range from 400 nm to 700 nm is not more than 2. A method according to any one of claims 1 to 3, wherein the ink repellent Layer is a silicone rubber layer. Direct writable planographic printing plate precursor, the at least one substrate, a heat-sensitive layer and an ink repellent layer in this order, wherein the precursor an ultraviolet absorption spectrum using the transmission method is examined, having the following characteristics: (1) the main peak of the ultraviolet absorption spectrum is intermediate 700 nm and 1200 nm, and (2) the ratio A: B between the absorbency at 830 nm (A) and the absorbance at 650 nm (B) is not less than 3.0. Direct writable planographic printing plate precursor after Claim 5, whose maximum absorption capacity in the wavelength range from 400 to 700 nm is not more than 2. Direct writable planographic printing plate precursor after Claim 5 or 6, wherein the ink repellent layer has a Silicone rubber layer is. Direct writable planographic printing plate, at least a substrate, a heat-sensitive one Layer and an ink repellent layer in this order wherein the printing plate has an ultraviolet absorption spectrum, which is examined by means of the transmission method, with the having the following features: (1) the main peak of the ultraviolet absorption spectrum between 700 nm and 1,200 nm, and (2) the ratio A: B between the absorption capacity at 830 nm (A) and the absorbance at 650 nm (B) is not less than 3.0. Directly recordable planographic printing plate according to claim 8, whose maximum absorption capacity in the wavelength range from 400 to 700 nm is not more than 2. Directly recordable planographic printing plate according to claim 8 or 9, wherein the ink repellent layer is a silicone rubber layer is. Direct writable planographic printing plate after one the claims 8 to 10, wherein the heat-sensitive Layer in the printing area contains a printing ink, which has an absorption maximum in the range of 400 nm to 700 nm, and wherein the difference between the reflected absorption of the non-pressure area and the reflected absorption of the pressure range, observed at the maximum Absorption wavelength of the dye, not less than 0.3 and not more than 2.0. Directly recordable planographic printing plate according to claim 11, wherein the maximum absorption wavelength of the dye in the range from 500 to 650 nm.