EP0776770A1 - Support d'aluminium ou ses alliages avec une couche hydrophile et procédé pour sa préparation - Google Patents

Support d'aluminium ou ses alliages avec une couche hydrophile et procédé pour sa préparation Download PDF

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Publication number
EP0776770A1
EP0776770A1 EP96118352A EP96118352A EP0776770A1 EP 0776770 A1 EP0776770 A1 EP 0776770A1 EP 96118352 A EP96118352 A EP 96118352A EP 96118352 A EP96118352 A EP 96118352A EP 0776770 A1 EP0776770 A1 EP 0776770A1
Authority
EP
European Patent Office
Prior art keywords
layer
basic
weight
support material
hydrophilizing
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.)
Withdrawn
Application number
EP96118352A
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German (de)
English (en)
Inventor
Werner Riedel
Michael Brenk
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hoechst AG
Original Assignee
Hoechst AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Hoechst AG filed Critical Hoechst AG
Publication of EP0776770A1 publication Critical patent/EP0776770A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/18—After-treatment, e.g. pore-sealing
    • C25D11/24—Chemical after-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • B05D7/16—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies using synthetic lacquers or varnishes
    • 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
    • B41N3/036—Chemical or electrical pretreatment characterised by the presence of a polymeric hydrophilic coating

Definitions

  • the invention relates to a mechanically and / or electrochemically roughened and optionally anodically oxidized support material made of aluminum or its alloys, with a hydrophilizing layer of at least one polymer with basic and acidic centers and a process for producing the support material.
  • Carrier materials for offset printing plates are provided with a light-sensitive layer (copying layer), with the help of which a printing image is generated by photomechanical means. After the printing image has been produced, the support carries the printing image areas and at the same time forms the hydrophilic image background for the lithographic printing process in the non-image areas (non-image areas).
  • the carrier material is additionally hydrophilized, because otherwise it would not accept enough water.
  • the hydrophilizing agent must be matched to the respective light-sensitive layer in order to avoid undesired reactions and not to impair the adhesion.
  • the known hydrophilization methods have more or less major disadvantages.
  • the photosensitive layers After treatment with alkali silicates, which lead to good developability and hydrophilicity, the photosensitive layers must deteriorate after a long period of storage.
  • carrier materials with water-soluble polishes their good solubility - especially in aqueous-alkaline developers, as they are mainly used to develop positive-working layers - leads to a marked weakening of the hydrophilizing effect.
  • Highly sensitive layers which are used for imaging with lasers (EP-A 0 364 735) and which are a polymer binder, a free-radically polymerizable compound with at least one polymerizable group and a photo-reducing dye, a trihalomethyl compound which can be cleaved by radiation and are particularly susceptible to the formation of color fog contain a metallocene compound as photoinitiators. There are therefore particularly high demands on the hydrophilic Carrier material placed in such a way that no components of the layer may remain at the non-image locations.
  • the carrier material is coated with a homopolymer of acrylamidoisobutylenephosphonic acid or a copolymer of acrylamidoisobutylenephosphonic acid and acrylamide or with a salt of this homo- or copolymer with an at least divalent metal cation.
  • the coating has the advantage that the finished printing plates show good hydrophilicity at the non-image areas and have a reduced color haze.
  • EP-A 0 490 231 describes the treatment of printing plate supports with polyethyleneimines which contain structural elements of the type - (CH 2 -CH 2 -N (X) -) n - or with polyvinylamines, the structural elements of the type - (CH 2 -CH (NY 1 Y 2 ) -) n - contain, where X, Y 1 and Y 2 are optionally C-substituted sulfomethyl groups or phosphonomethyl groups. But also with this procedure optimal results are not yet achieved.
  • the unpublished DE 44 23 140.7 describes a process which works with the substances listed in EP-A 0 490 231 in a first step and with other phosphonic acid compounds in a second step.
  • the process has the disadvantage that it has to be carried out in two steps in a complex manner.
  • the object is achieved by a mechanically and / or electrochemically roughened and optionally anodically oxidized support material made of aluminum or its alloys, with a hydrophilizing layer of at least one polymer with basic and acidic centers in such a way that the hydrophilizing layer consists of a mixture of two components , of which one component belongs to the group of amino acids and the other component belongs to the polymers with basic and acidic centers.
  • the process for producing the support material is characterized in that in a one-step process a hydrophilizing layer containing two components is applied to the mechanically and / or electrochemically roughened and optionally anodically oxidized support material made of aluminum or its alloys in aqueous solution. Further process steps are described in claims 9 to 13.
  • the hydrophilizing layer can be applied by spraying on an appropriate solution.
  • concentration of the hydrophilizing compounds in this solution can vary within wide limits, but solutions with a concentration of 0.1 to 20 g / l, preferably 0.3 to 5 g / l, have proven to be particularly advantageous. These quantities apply to both components.
  • the material can be rinsed off to remove the unnecessary hydrophilizing agent.
  • the hydrophilization can take place at temperatures of 20 to 95 ° C, but temperatures of 30 to 65 ° C are preferred.
  • the material to be coated is generally sprayed or immersed for 1 to 5 minutes. It is disadvantageous if the treatment time is shorter than 1 s, but not if it is more than 5 min.
  • the coated carrier is expediently dried at temperatures from 100 to 130 ° C.
  • modified polyethyleneimine and the modified polyvinylamine and processes for their preparation are described in EP-A 0 490 231. They are usually produced from the corresponding unmodified precursors by phosphonomethylation and / or sulfonomethylation.
  • the carrier materials according to the invention can then be coated with various light-sensitive mixtures.
  • all mixtures are suitable which produce layers which, after imagewise exposure, subsequent development and / or fixing, give a positive or negative image.
  • the material suitable as a printing plate retains its excellent hydrophilicity and practically no longer shows any color veils.
  • the present invention also relates to a recording material with a carrier material made of aluminum or its alloys, which is hydrophilized and coated with a radiation-sensitive layer.
  • 0.3 mm thick bright rolled aluminum (DIN material no. 3.0255) was degreased with a 2% aqueous NaOH pickling solution at a temperature of 50 to 70 ° C.
  • the surface was then electrochemically roughened using alternating current in an electrolyte containing HNO 3 .
  • the R z value of the surface roughness was then 6 ⁇ m.
  • the subsequent anodic oxidation was carried out in an electrolyte containing sulfuric acid.
  • the oxide layer weight was approximately 3.0 g / m 2 .
  • 0.3 mm thick bright rolled aluminum (DIN material no. 3.0515) was degreased with a 2% aqueous NaOH pickling solution at a temperature of 50 to 70 ° C.
  • the surface was electrochemically roughened using alternating current in an electrolyte containing hydrochloric acid.
  • the R z value of the surface roughness was then 6 ⁇ m.
  • the subsequent anodic oxidation was carried out in an electrolyte containing sulfuric acid.
  • the oxide layer weight was approximately 2.0 g / m 2 .
  • 0.2 mm thick bright rolled aluminum (DIN material no. 3.0255) was degreased with a 2% aqueous NaOH pickling solution at a temperature of 50 to 70 ° C and then mechanically roughened with cutting grains (e.g. quartz powder or aluminum oxide). The R z value of the surface roughness was then 4 ⁇ m. The subsequent one anodic oxidation was carried out in an electrolyte containing phosphoric acid. The oxide layer weight was about 0.9 g / m 2 .
  • a carrier is treated as described under type 2, but anodized to an oxide layer weight of 1.5 g / m 2 .
  • the following examples show the advantages of the carrier material according to the invention.
  • the hydrophilizations A * to D * according to Table 1 were used for the comparative experiments, while the support material according to the invention was hydrophilized according to E.
  • the basic centers in the polymer containing basic and acidic centers are primary, secondary or tertiary amino groups, while the acidic centers are carboxy, phosphono or sulfo groups.
  • the pH of the polymer is in the range from 4 to 9, in particular from 4.5 to 7.5.
  • One component of the hydrophilizing layer is selected, for example, from the group of sulfonated or phosphonomethylated polyethyleneimine and polyvinylamine. This component can also be a copolymer or terpolymer from the group consisting of substituted aminoacrylates, vinylpyrrolidones, vinylimidazoles.
  • the other component of the hydrophilizing layer is selected, for example, from the group of monobasic amino acids, such as glycine, aminohexanoic acid, aminobenzoic acid, diaminobenzoic acid, leucine. Further additives are listed in Examples 6 to 34 under the letters N to S. Table 1 Hydrophilization A * None B * with polyvinylphosphonic acid (2 g / l at 75 ° C, pH 2) C * with N-phosphonomethyl-polyethyleneimine (1 g / l at 65 ° C, pH 4.5) D * first C), then B) E according to the invention as C *, additionally 1 g / l glycine in the solution
  • the plates were contacted in a vacuum contact copier frame by evacuation with a test assembly, exposed with a metal halide-doped 5 kW mercury vapor lamp at a distance of 110 cm so that after development an open step 4 resulted in the UGRA offset test wedge, which resulted in high exposure for film edge removal.
  • a developing device VA86 from Hoechst AG
  • the occurrence of residual layer haze is investigated after a developer load of 4 m 2 per liter of developer.
  • step E of the carrier according to the invention proved to be more advantageous and easier to carry out.
  • the plate was then coated with a layer of polyvinyl alcohol, exposed and developed.
  • Examples 6 to 34 (Table 5/6) are intended to show the superiority of the supports according to the invention over the supports of Comparative Examples V6 to V37 which have been hydrophilized according to Table 1, A to D.
  • the recording materials produced according to the conditions given in the tables were examined as follows:
  • color veils are visible from a measured value of around 0.8. In any case, they represent a cosmetic defect in the printing plate and can therefore lead to complaints by the buyers. Should the color veil become very intense, this is an indication of a large amount of layer residues in the non-image areas, which may lead to undesired printing (toning), especially if, as is often desired, little dampening solution is dosed. An exact value of the color veil for this case cannot be given.
  • the non-image area of a printing plate was treated with a commercially available correction agent.
  • the brightnesses were then measured, once in the corrected and once in the uncorrected area.
  • the difference dL * 2 was also formed here. Is it significantly different from 0, i.e. in the range from 0.5 to 1, the correction agent could either still remove layer residues from the surface or even attacked and damaged the surface of the non-image area itself.
  • the non-image area of a printing plate was coated with ink via a rubber hand roller, brought into dilute phosphoric acid and the time taken for the dilute phosphoric acid to detach the ink from the non-image area. This time must not exceed 30 s for a well hydrophilic carrier.
  • the usually acidic dampening solution used in the printing process is simulated with the dilute phosphoric acid.
  • Carriers of types 1 and 2 were anodized and subjected to a hydrophilizing treatment in an immersion bath for 5 seconds.
  • the conditions are given in Table 3.
  • the type of hydrophilizing treatment is given in column 2 of Tables 3 to 6 below. The designation given there corresponds to that in Table 1.
  • the plates were coated with the solution given in Example 1, exposed and developed with a developer of types 1 and 2 in the above-mentioned developing device VA86.
  • Table 3 shows that the printing plates not produced according to the invention have a sufficiently good hydrophilicity in the non-image areas, but either have a clear color haze or else one Suffer from the correction agent, which leads to discoloration in the non-image areas, or both phenomena.
  • two different carrier types were used and two different developers were used, none of the combinations mentioned in the table is able to achieve good results in all properties.
  • the hydrophilizing treatment brings tolerably good results, but this is a two-stage process, which has technical disadvantages.
  • the recording materials according to Table 4 were produced with a type 2 support. They were subjected to a hydrophilizing treatment not according to the invention, i.e. immersed in an aqueous solution containing phosphonomethylated polyimine as a component and another additive. The concentration of the polyimine was 1 g / l in all cases.
  • the type of the second component and the treatment temperature are given in the following list.
  • Table 5 shows results with type 2 carriers and table 6 those with type 4 carriers. They were subjected to a hydrophilizing treatment according to the invention, i.e. immersed in an aqueous solution containing phosphonomethylated polyimine as one component and an amino acid as another additive.
  • concentration 1 concentration of the polyimine
  • concentration 2 concentration of the second component
  • the type of the second component and the treatment temperature are given in the following list.
  • the dive time was 5 s in most cases. Diving times from 15 s to a few minutes have the same effect. However, the dive time should not be less than 1 s.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Printing Plates And Materials Therefor (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
EP96118352A 1995-11-25 1996-11-15 Support d'aluminium ou ses alliages avec une couche hydrophile et procédé pour sa préparation Withdrawn EP0776770A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE1995143934 DE19543934A1 (de) 1995-11-25 1995-11-25 Trägermaterial aus Aluminium oder seinen Legierungen, mit einer hydrophilierenden Schicht, und Verfahren zur Herstellung des Trägermaterials
DE19543934 1995-11-25

Publications (1)

Publication Number Publication Date
EP0776770A1 true EP0776770A1 (fr) 1997-06-04

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EP96118352A Withdrawn EP0776770A1 (fr) 1995-11-25 1996-11-15 Support d'aluminium ou ses alliages avec une couche hydrophile et procédé pour sa préparation

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EP (1) EP0776770A1 (fr)
JP (1) JPH09204048A (fr)
DE (1) DE19543934A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102012008214B4 (de) 2011-10-18 2022-03-03 Leibniz-Institut Für Polymerforschung Dresden E.V. Verfahren zur stoffschlüssigen Verbindung von Bauteilen, eine mit dem Verfahren hergestellte stoffschlüssige Verbindung sowie eine Verwendung des Verfahrens

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3276868A (en) 1960-08-05 1966-10-04 Azoplate Corp Planographic printing plates
US4153461A (en) 1967-12-04 1979-05-08 Hoechst Aktiengesellschaft Layer support for light-sensitive material adapted to be converted into a planographic printing plate
EP0069320A1 (fr) 1981-07-06 1983-01-12 Hoechst Aktiengesellschaft Matériaux de support pour plaques lithographiques, aux propriétés hydrophiles améliorées, procédés pour leur fabrication, et leur utilisation
EP0190643A2 (fr) 1985-02-08 1986-08-13 Hoechst Aktiengesellschaft Matériau de supports hydrophilisés pour plaques d'impression offset, procédé de fabrication et leur emploi
US4801527A (en) * 1984-01-17 1989-01-31 Fuji Photo Film Co., Ltd. Presensitized O-quinone diazide plate having an anodized aluminum base with an amine compound containing hydrophilic layer
EP0364735A1 (fr) 1988-09-21 1990-04-25 Hoechst Aktiengesellschaft Mélange photopolymérisable et matériau d'enregistrement fabriqué à partir de celui-ci
EP0490231A2 (fr) 1990-12-14 1992-06-17 BASF Aktiengesellschaft Dérivés de polyethyleneimine et polyvinylamine, supports à base d'aluminium recouverts de ceux-ci et leur utilisation dans la fabrication de plaques offset
DE4406279A1 (de) * 1993-02-25 1994-09-01 Fuji Photo Film Co Ltd Aluminiumsubstrat für eine lithographische Druckplatte

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3276868A (en) 1960-08-05 1966-10-04 Azoplate Corp Planographic printing plates
US4153461A (en) 1967-12-04 1979-05-08 Hoechst Aktiengesellschaft Layer support for light-sensitive material adapted to be converted into a planographic printing plate
EP0069320A1 (fr) 1981-07-06 1983-01-12 Hoechst Aktiengesellschaft Matériaux de support pour plaques lithographiques, aux propriétés hydrophiles améliorées, procédés pour leur fabrication, et leur utilisation
US4801527A (en) * 1984-01-17 1989-01-31 Fuji Photo Film Co., Ltd. Presensitized O-quinone diazide plate having an anodized aluminum base with an amine compound containing hydrophilic layer
EP0190643A2 (fr) 1985-02-08 1986-08-13 Hoechst Aktiengesellschaft Matériau de supports hydrophilisés pour plaques d'impression offset, procédé de fabrication et leur emploi
EP0364735A1 (fr) 1988-09-21 1990-04-25 Hoechst Aktiengesellschaft Mélange photopolymérisable et matériau d'enregistrement fabriqué à partir de celui-ci
EP0490231A2 (fr) 1990-12-14 1992-06-17 BASF Aktiengesellschaft Dérivés de polyethyleneimine et polyvinylamine, supports à base d'aluminium recouverts de ceux-ci et leur utilisation dans la fabrication de plaques offset
DE4406279A1 (de) * 1993-02-25 1994-09-01 Fuji Photo Film Co Ltd Aluminiumsubstrat für eine lithographische Druckplatte

Also Published As

Publication number Publication date
JPH09204048A (ja) 1997-08-05
DE19543934A1 (de) 1997-05-28

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