EP0089510B1 - Matériau à base d'aluminium avec une couche superficielle hydrophile, un procédé pour sa préparation et son utilisation comme support pour des plaques d'impression lithographiques - Google Patents

Matériau à base d'aluminium avec une couche superficielle hydrophile, un procédé pour sa préparation et son utilisation comme support pour des plaques d'impression lithographiques Download PDF

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Publication number
EP0089510B1
EP0089510B1 EP83101813A EP83101813A EP0089510B1 EP 0089510 B1 EP0089510 B1 EP 0089510B1 EP 83101813 A EP83101813 A EP 83101813A EP 83101813 A EP83101813 A EP 83101813A EP 0089510 B1 EP0089510 B1 EP 0089510B1
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EP
European Patent Office
Prior art keywords
acid
aqueous solution
salts
salt
solution
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.)
Expired
Application number
EP83101813A
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German (de)
English (en)
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EP0089510A1 (fr
Inventor
John E. Walls
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CNA Holdings LLC
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American Hoechst Corp
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41N—PRINTING PLATES OR FOILS; MATERIALS FOR SURFACES USED IN PRINTING MACHINES FOR PRINTING, INKING, DAMPING, OR THE LIKE; PREPARING SUCH SURFACES FOR USE AND CONSERVING THEM
    • B41N3/00—Preparing for use and conserving printing surfaces
    • B41N3/03—Chemical or electrical pretreatment
    • B41N3/038—Treatment with a chromium compound, a silicon compound, a phophorus compound or a compound of a metal of group IVB; Hydrophilic coatings obtained by hydrolysis of organometallic compounds

Definitions

  • the invention relates to a plate, film or tape-shaped material made of roughened aluminum or one of its alloys with a hydrophilic surface coating based on at least one compound having at least one ionogenic group. It also relates to a process for the production of this material and its use in the production of offset printing plates bearing a radiation-sensitive layer.
  • the basic procedure is to provide the surface of the metal carrier with a coating before the application of the radiation-sensitive coating composition, which then results in the image areas of the printing surface of the printing form after exposure and development the later non-image areas of the printing form) are hydrophilized and, on the other hand, there is a good interaction both with the metal support and with the image areas.
  • EP-A 0 048 909 and EP-A 0 050 216 [prior art according to Article 54 (3) EPC], methods for the anodic oxidation of plate, foil or strip material made of aluminum or its alloys are known, which are described in an aqueous, preferably polybasic organic acids or esters of polybasic inorganic acids with free acid groups containing electrolytes.
  • the polybasic organic acids are polymers such as polyvinylphosphonic acid, polybenzenesulfonic acid or polyacrylic acid.
  • Esters include, for example, phytic acid, dodecyl-naphthalene-disulfonic acid or ethylenediaminetetraacetic acid to monomeric polybasic organic acids.
  • the process products are preferably used as carrier material in the production of offset printing plates bearing a radiation-sensitive layer.
  • silicates both electrochemically and thermally is a process for the production of «ceramic-like», non-porous, hydrophilic layers on aluminum, which is particularly suitable for substrates that are sensitive to radiation to be coated by the consumer and, to a lesser extent, for offset printing plates that are sensitive to industrial radiation is.
  • the clearest advantages of the silicating process are the rapid freewheeling of the printing forms due to the “ceramic-like” nature of their surface and the storage stability over long periods without loss of hydrophilicity before the radiation-sensitive coating is applied.
  • the alkaline nature of the sodium silicate used storage problems can occur with plates that are already sensitive to radiation, this also applies if they are rinsed off well before applying a radiation-sensitive coating.
  • Treatments with organic acids such as polyvinylphosphonic acid have the advantage that they produce an acidic surface which is particularly well tolerated with negative-working radiation-sensitive layers containing diazonium compounds. Both thermal and electrochemical processes result in better adhesion between the roughened aluminum surface and the applied radiation-sensitive layer and thus lead to better printing behavior.
  • This advantageous effect of the organic acid may be due to the fact that it chemically interacts with the aluminum and with the molecules of the radiation-sensitive coating, with a certain probability through covalent bonding in the former and ionic bonding in the latter, which also excellent Storage-ready radiation-sensitive pre-coated printing plates result.
  • the surfaces hydrophilized with these acids also have some disadvantages.
  • the prepared surface must not be stored for too long between the time of manufacture and the time of the radiation-sensitive coating, that the hydrophilicity is sometimes not as good as that of silicate-coated plates and that the printing formes do not always have the ability to run freely and stay clean in the non-image areas, especially if the printing machine is switched off for a longer period during the printing process.
  • the salts according to b) are prepared from aqueous solutions of the acids or acidic esters by titration with an aqueous alkali or ammonium hydroxide solution until an alkaline pH is reached.
  • the coating applied to the material can serve, for example, as a corrosion-resistant surface, as a dielectric, as a barrier layer or, in particular, as a hydrophilizing intermediate layer in the production of offset printing plates from a support and a radiation-sensitive coating. It has been shown that the treatment of at least one surface of an aluminum material of the type described above with the mixture forming a “ceramic-like” layer according to this invention gives the surface favorable properties which, in its overall structure, are particularly suitable for use as supports for offset printing plates, but also make it suitable as part of capacitors.
  • the production of the material according to the invention is based on aluminum or its alloys, including, for example, those with a content of more than 98.5% of Al and proportions of Si, Fe, Ti, Cu and Zn.
  • the materials are still roughened mechanically (e.g. by brushing and / or with abrasive treatments), chemically (e.g. by etching agents) and / or electrochemically (e.g. by AC treatment in aqueous acid or salt solutions).
  • This roughening stage can also be followed by an anodic oxidation, for example in order to improve the abrasion and adhesion properties of the surface.
  • the acids or acidic esters suitable according to the invention preferably include the polymeric compounds such as polyvinylphosphonic acid, polyvinylsulfonic acid, hydrolyzed copolymers of methyl vinyl ether and maleic anhydride, polybenzene phosphonic acid (condensation product from benzenephosphonic acid and formaldehyde), polystyrene sulfonic acid, polydiisopropylbenzenesulfonic acid and condensation product from diisulfonic acid , Polyacrylic acid or polymethacrylic acid, but also monomeric compounds such as phytic acid, 2-ethylhexanephosphonic acid, mellitic acid or pyromellitic acid.
  • polymeric compounds such as polyvinylphosphonic acid, polyvinylsulfonic acid, hydrolyzed copolymers of methyl vinyl ether and maleic anhydride, polybenzene phosphonic acid (condensation product from benzenephosphonic acid and formaldehy
  • Suitable hydroxides include potassium, lithium, sodium and ammonium hydroxide. It is preferably titrated until a pH of at least 8.0, in particular from about 8.0 to 10.5, is reached. It is also important that the acid is selected and the titration is carried out up to a pH such that the titration product is obtained as an aqueous solution and no precipitate forms when this product is mixed with the silicates and / or borates to be used in the coating solution becomes.
  • the titration product will then be there mixed with compatible silicates and borates so that an aqueous solution results.
  • the silicates can be sodium, potassium and lithium salts, which are most suitable if they have a SiO z : Na 2 O ratio of at least 1: 1, in particular at least 2: 1 and preferably at least 2.5: 1 , exhibit.
  • Sodium silicate, sodium fluoroborate and sodium metaborate are most suitable for offset printing plate supports. If you only want to achieve improved corrosion resistance, other suitable compounds are ammonium pentaborate, potassium and sodium tetraborate. In general, sodium, lithium, potassium and ammonium tetra and pentaborates are preferred for the borates.
  • the starting base for component b) or a) is an aqueous solution of the acid or of the acidic ester at a concentration of 1 to 80 g / l, in particular from 5 to 40 g / l and preferably from 10 to 20 g / l.
  • the solution of the acid or of the acidic ester is titrated with an aqueous alkali or ammonium hydroxide solution to an alkaline pH, preferably to a pH of 8.0 to 10.5.
  • the titration product is then admixed with the silicate or borate in a proportion of 5 to 120 g / l, in particular 15 to 80 g / l and preferably 40 to 70 g / l.
  • an aqueous polyvinylphosphonic acid solution in a concentration of 10 g / l is titrated with an aqueous ammonium hydroxide solution to a pH of 9.5 and mixed with 70 g / l of solid sodium silicate, in which the ratio SiO z : Na 2 0 is approximately 2.5: 1.
  • the aluminum material described above is then treated continuously or discontinuously with the coating solution prepared in this way in a belt system.
  • This treatment can be chemical (i.e. non-electrochemical) or electrochemical, with the electrochemical treatment providing the preferred surface.
  • the aluminum plate can either be sprayed with the coating solution or immersed in it, while the solution is at a temperature of 60 to 100 ° C., in particular 75 to 100 ° C. and preferably 85 to 100 ° C. is held.
  • the treatment should last at least 20 seconds, with a treatment duration beyond 60 seconds no further significant improvement in the surface is found.
  • the aluminum is immersed as an anode in a bath from the coating solution.
  • the temperature of the solution is kept above its solidification point and is generally 5 to 90 ° C., in particular 10 to 60 ° C. and preferably 20 to 40 ° C.
  • the cathode made of lead for example, is immersed in the solution so that it is at a distance of 2 to 75 cm from the anode.
  • the cathode / anode distance is in particular 5 to 25 cm, preferably 10 to 15 cm.
  • Direct current or pulsating current is applied, which can have a voltage of 1 to 120 V or higher as long as no arcing occurs.
  • the voltage is preferably 10 to 90 V, in particular 20 to 30 V; the current density is generally between 3 and 30 A / dm 2 .
  • the best surface is obtained when acidic, ie with a dilute aqueous solution of an acid such as phosphoric acid or sulfuric acid, is rinsed in order to re-form the acid form from the salts. But even without this transformation, ie by rinsing with water alone, the surface fulfills its purpose.
  • the aluminum surface thus hydrophilized and provided with an intermediate layer is coated on one or both sides with a radiation-sensitive composition suitable for offset printing.
  • the printing plate is irradiated by a photographic original, developed and used as a printing form on a printing press for producing numerous prints from an original.
  • the usual radiation-sensitive reproduction layers which are suitable for offset printing purposes and which react to actinic light and UV light or other radiation sources when irradiated can be used to good effect for the practice of this invention.
  • the radiation-sensitive reproduction layer can also contain resinous binders such as polyvinyl formal resins or phenol / cresol formaldehyde resins. Further constituents can be the surfactants, UV absorbers, dyes and fillers known to the person skilled in the art.
  • the rate of dissolution of the layer in sec in a saturated aqueous SnC1 2 solution is a measure of the alkali resistance and density of a layer on aluminum.
  • the layer is more alkali-resistant the longer it takes to dissolve it.
  • the layer thicknesses should be roughly comparable, since of course they also represent a parameter for the dissolution rate.
  • a drop of a solution of a saturated aqueous SnC1 2 solution is brought onto the surface to be examined and the period of time until the appearance of metallic tin is determined, which can be recognized by a dark color.
  • the layer weight of the intermediate layer produced according to the invention can be determined quantitatively by stripping in an aqueous chromic acid / phosphoric acid standard solution (1.95% Cr0 3 , 3.41% H 3 P0 4 - 85%) at approx. 82 ° C. in 15 minutes .
  • a coating of a layer weight of 350 mg is applied / m 2 generated.
  • the plate is rinsed well and patted dry. With the surface produced in this way, the SnCi z takes 101 seconds until it has completely migrated through the electrochemically produced surface coating.
  • the plate is dyed dry, after which the printing ink can be easily removed from the surface by rinsing it gently with water. Plates produced in the same way are aged at room temperature, and after 7 days one of these plates is dyed dry, after which the ink can be removed again. After 10 days of aging, on the other hand, it is more difficult to remove the ink, and after 14 days the ink cannot be removed at all.
  • One of the non-aged plates is coated with a negative working radiation sensitive solution which contains a pigment, about 7.5 parts by weight of a polyvinyl formal resin and about 2.5 parts by weight of a polycondensation product made of 3-methoxy-diphenylamine.
  • a negative working radiation sensitive solution which contains a pigment, about 7.5 parts by weight of a polyvinyl formal resin and about 2.5 parts by weight of a polycondensation product made of 3-methoxy-diphenylamine.
  • a negative working radiation sensitive solution which contains a pigment, about 7.5 parts by weight of a polyvinyl formal resin and about 2.5 parts by weight of a polycondensation product made of 3-methoxy-diphenylamine.
  • the fountain solution supply is interrupted several times during the operation of the printing press, so that the printing ink is rolled up over the entire surface of the plate.
  • the dampening roller is then switched on again and observed how quickly and completely the printing ink disappears from the plate background.
  • the color is easy to remove on the first try, but takes longer on the second try, but is successful.
  • On the third try the plate tones and it is no longer possible to print properly.
  • the background In order to be able to continue printing with good quality, the background must first be cleaned with a cleaning liquid.
  • Another plate sample is provided with the radiation-sensitive coating 48 hours after the surface coating has been produced. The plate is divided into individual subsamples, all of which are aged at 100 ° C., samples being taken and evaluated every 30 minutes. This process product still proves to be useful up to an aging period of about 4.5 hours.
  • Comparative example V2 is carried out as described in comparative example V1, but instead of an electrochemical treatment, an immersion treatment is carried out in an aqueous PVPS solution.
  • Comparative example V3 is carried out as described in comparative example V2, but an aqueous sodium silicate solution is used.
  • Comparative example V4 is carried out as described in comparative example V1, but an aqueous sodium silicate solution is used.
  • Comparative example V5 is carried out as described in comparative example V1 1, but an aqueous solution of the titration product of PVPS and ammonium hydroxide is used.
  • Examples 1, 3, 4, 7 and 9 are carried out according to the details of comparative example V1 1, but a solution with a content according to the invention is used as the electrolyte (see table).
  • Examples 2 and 5 are carried out as described in Comparative Example V2, but a solution with a content according to the invention is used in the immersion bath (see table).
  • Example 6 is carried out according to the details of comparative example V1, but the process is carried out at a temperature below the range claimed according to the invention.
  • Example 8 is carried out as described in Example 5, but the surface is treated electrochemically.
  • the coated plate has a good number of copies and a good aging behavior; in these comparative examples, only polyvinylphosphonic acid is contained in the hydrophilizing treatment solution. Plates with good aging behavior of the not yet radiation-sensitive coated carrier and good behavior in the toning test repeated at regular intervals, which indicates a high hydrophilicity of the carrier, can be found in Comparative Examples V3 and V4, in which an aqueous sodium silicate solution is used.
  • the conditions of comparative example V1 are reproduced in comparative example V5, but the pH is adjusted to 9.5 with an aqueous ammonium hydroxide solution.
  • Example 7 a solution according to the invention is used for the electrochemical process, so that a direct comparison with comparative examples V1 and V4 is possible. It is shown that all of the results of Example 7 which are relevant to the field of offset printing are better than in the comparison.
  • a solution of the same content is used at different temperatures in order to demonstrate the importance of higher temperatures for the immersion process and lower temperatures for the electrochemical process variant. Although the results of these tests are generally acceptable to good, the electrochemical process variant is significantly better if it is carried out at lower temperatures, while the immersion process gives better results.
  • Examples 1 to 4 and 9 illustrate further embodiment variants of the invention, in which work is carried out either electrochemically or in the immersion process.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Printing Plates And Materials Therefor (AREA)
  • Chemical Treatment Of Metals (AREA)

Claims (16)

1. Matériau en forme de plaques, de feuilles ou de rubans, en aluminium ou en un de ses alliages, grainé chimiquement, mécaniquement et/ou électrochimi- quement, avec un revêtement superficiel hydrophile appliqué sur une face ou sur les deux à base d'au moins un composé chimique présentant au moins un groupement fonctionnel ionogène, caractérisé par le fait que le revêtement superficiel hydrophile contient un mélange
a) d'au moins un sel avec un anions silicate, fluoroborate, tétraborate ou pentaborate et un cation monovalent, et
b) d'au moins un sel alcalin ou d'ammonium, à réaction alcaline en solution aqueuse, d'un acide sulfonique, phosphonique ou carboxylique au moins tribasique, ou d'un ester d'acide phosphorique présentant encore au moins un groupement fonctionnel acide, qui ne forme aucun dépôt insoluble avec le sel de a) en solution aqueuse.
2. Matériau selon la revendication 1, caractérisé par le fait qu'il est oxydé par voie anodique.
3. Matériau selon l'une des revendications 1 ou 2, caractérisé par le fait qu'il est soumis à un stade de rinçage ultérieur acide.
4. Matériau selon l'une des revendications 1 à 3, caractérisé par le fait que les sels suivant b) sont préparés à partir de solutions aqueuses des acides ou des esters acides par titrage avec une solution aqueuse d'hydroxyde d'ammonium ou d'hydroxyde alcalin jusquà l'obtention d'un pH alcalin.
5. Matériau selon la revendication 4, caractérisé par le fait que les solutions aqueuses contennent 1 à 80 g/I d'acides ou d'esters acides et que le pH a une valeur de 8,0 à 10,5.
6. Matériau selon l'une des revendications 1 à 5, caractérisé par le fait que les sels suivant b) sont des sels de sodium, de lithium, de potassium ou d'ammonium des composés polymères acide polyvinylphos- phonique, acide polyvinylsulfonique, copolymère hydrolysé d'éther méthylvinylique et d'anhydride d'acide maléique, acide polybenzènephosphonique, acide polystyrènesulfonique, acide poly-diisopropyl- benzènesulfonique, acide polyacrylique ou acide polyméthacrylique.
7. Matériau selon l'une des revendications 1 à 5, caractérisé par le fait que les sels suivant b) sont des sels de sodium, de lithium, de potassium ou d'ammonium des composées monomères acide phytinique, acide 2-éthyl-hexanephosphonique, acide mellique ou acide pyromellique.
8. Matériau selon l'une des revendications 1 à 7, caractérisé par le fait que les sels suivant a) sont des silicates de sodium, de potassium ou de lithium, le pentaborate d'ammonium, le tétraborate de potassium ou le fluoroborate de sodium.
9. Procédé pour la préparation d'un matériau selon l'une des revendications 1 à 8, caractérisé par le fait que pour le revêtement superficiel
a) une solution aqueuse à réaction alcaline est préparée à partir d'au moins un sel alcalin ou d'ammonium d'un acide sulfonique, phosphonique ou carboxylique au moins tribasique, ou d'un ester d'acide phosphonique présentant encore au moins un groupement fonctionnel acide,
b) à cette solution est mélangé au moins un sel avec un anion silicate, fluoroborate, tétraborate ou pentaborate et un cation monovalent sans formation d'un dépôt insoluble,
c) la solution contenant le mélange de a) et b) est mise à réagir avec au moins une surface du matériau d'aluminium ou d'un de ses alliages.
10. Procédé selon la revendication 9, caractérisé par le fait que le sel selon le stade b) est mélangé en solution aqueuse.
11. Procédé selon l'une des revendications 9 ou 10, caractérisé par le fait que le revêtement superficiel est en outre rincé avec une solution aqueuse acide.
12. Procédé selon l'une des revendications 10 à 11, caractérisé par le fait que les sels suivants b) sont utilisés en solution aqueuse à une teneur de 5 à 120 g/I.
13. Procédé selon l'une des revendications 9 à 12, caractérisé par le fait que le stade c) est effectué par immersion pendant au moins 20 secondes à une température de 60 à 100°C.
14. Procédé selon l'une des revendications 9 à 12, caractérisé par le fait que le stade c) est effectué par voie électrochimique pendant au moins 5 secondes à une température de 5 à 90°C.
15. Procédé selon la revendication 14, caractérisé par le fait que l'on utilise un courant continu d'une densité de courant de 3 à 30 A/dm2.
16. Utilisation du matériau selon l'une des revendications 1 à 8 en tant que matériau de support dans la préparation de plaques offset portant une couche sensible aux radiations.
EP83101813A 1982-03-18 1983-02-24 Matériau à base d'aluminium avec une couche superficielle hydrophile, un procédé pour sa préparation et son utilisation comme support pour des plaques d'impression lithographiques Expired EP0089510B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US359455 1982-03-18
US06/359,455 US4376814A (en) 1982-03-18 1982-03-18 Ceramic deposition on aluminum

Publications (2)

Publication Number Publication Date
EP0089510A1 EP0089510A1 (fr) 1983-09-28
EP0089510B1 true EP0089510B1 (fr) 1986-01-29

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EP83101813A Expired EP0089510B1 (fr) 1982-03-18 1983-02-24 Matériau à base d'aluminium avec une couche superficielle hydrophile, un procédé pour sa préparation et son utilisation comme support pour des plaques d'impression lithographiques

Country Status (5)

Country Link
US (1) US4376814A (fr)
EP (1) EP0089510B1 (fr)
JP (1) JPS58171574A (fr)
CA (1) CA1196840A (fr)
DE (1) DE3361946D1 (fr)

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Publication number Publication date
JPS58171574A (ja) 1983-10-08
EP0089510A1 (fr) 1983-09-28
CA1196840A (fr) 1985-11-19
DE3361946D1 (en) 1986-03-13
US4376814A (en) 1983-03-15

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