EP0683248B1 - Verfahren zur Nachbehandlung von platten-, folien- oder bandförmigem Material, Träger aus derartigem Material und seine Verwendung für Offsetdruckplatten - Google Patents
Verfahren zur Nachbehandlung von platten-, folien- oder bandförmigem Material, Träger aus derartigem Material und seine Verwendung für Offsetdruckplatten Download PDFInfo
- Publication number
- EP0683248B1 EP0683248B1 EP95107331A EP95107331A EP0683248B1 EP 0683248 B1 EP0683248 B1 EP 0683248B1 EP 95107331 A EP95107331 A EP 95107331A EP 95107331 A EP95107331 A EP 95107331A EP 0683248 B1 EP0683248 B1 EP 0683248B1
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- European Patent Office
- Prior art keywords
- post
- silicate
- process according
- ions
- layer
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- 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.)
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Classifications
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- 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
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- 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
- B41N1/00—Printing plates or foils; Materials therefor
- B41N1/04—Printing plates or foils; Materials therefor metallic
- B41N1/08—Printing plates or foils; Materials therefor metallic for lithographic printing
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- 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
- B41N3/034—Chemical or electrical pretreatment characterised by the electrochemical treatment of the aluminum support, e.g. anodisation, electro-graining; Sealing of the anodised layer; Treatment of the anodic layer with inorganic compounds; Colouring of the anodic layer
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- 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
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- 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
- C25D11/20—Electrolytic after-treatment
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- 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
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- 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
- B41N1/00—Printing plates or foils; Materials therefor
- B41N1/04—Printing plates or foils; Materials therefor metallic
- B41N1/08—Printing plates or foils; Materials therefor metallic for lithographic printing
- B41N1/083—Printing plates or foils; Materials therefor metallic for lithographic printing made of aluminium or aluminium alloys or having such surface layers
Definitions
- the invention relates to a process for the aftertreatment of plate, film or tape material based on chemically, mechanically and / or electrochemically roughened and anodically oxidized aluminum or one of its alloys, the aluminum oxide layers of which are treated with an alkali metal silicate in aqueous solution, and one Carrier made of such a material, in which the aluminum oxide layer is coated with an alkali metal silicate layer, and the use of such a carrier as a carrier for offset printing plates.
- Carrier materials for offset printing plates are either equipped directly by the consumer or by the manufacturer of precoated printing plates or equipped on one or both sides with a radiation or light-sensitive layer, a so-called reproduction layer, with the help of which an image to be printed is created for submission in a photomechanical way.
- the support After the radiation-sensitive layer has been exposed and developed, the support carries the image-bearing areas which later lead to color printing and, at the same time, forms the hydrophilic background for the lithographic printing process at the non-image areas during later printing, the so-called non-image areas.
- the parts of the radiation-sensitive layer which have become relatively more soluble after exposure must be easy to remove from the support without residue by development in order to produce the hydrophilic non-image areas.
- the carrier exposed in the non-image areas must have a high affinity for water, i.e. be highly hydrophilic in order to absorb water quickly and permanently during the lithographic printing process and to be sufficiently repellent to the bold printing ink.
- the adhesion of the radiation-sensitive layer before or the printing parts of the layer after the irradiation must be sufficient.
- Aluminum which is roughened on the surface by known methods by dry, wet brushing, sandblasting, chemical and / or electrochemical treatment, is used in particular as the base material for such layer supports.
- the roughened substrate is subjected to an anodization step to build up a thin oxide layer.
- the carrier materials in particular anodically oxidized carrier materials based on aluminum, are often used to improve the Layer adhesion, to increase the hydrophilicity and / or to facilitate the developability of the radiation-sensitive layers prior to the application of a radiation-sensitive layer, undergo a further treatment step, as described for example in EP-B 0 105 170 and EP 0 154 201.
- EP-B 0 105 170 discloses a process for the aftertreatment of aluminum oxide layers with an aqueous alkali silicate solution, in which after the treatment a) is carried out with an aqueous alkali silicate solution, a treatment b) is also carried out with a solution containing aqueous alkaline earth metal salts.
- the alkali silicate solution is an aqueous solution containing Na 2 SiO 3 .5 H 2 O. It is then rinsed with distilled water, this intermediate cleaning can also be omitted, and then, or immediately after the silicatization, treatment is carried out in an aqueous solution of an alkaline earth metal nitrate, such as calcium, strontium or barium nitrate.
- the intermediate rinses with distilled water show a certain influence on the alkali resistance, which is generally better for pores that have not been rinsed after the silicatization step than for rinsed pores.
- EP-B 0 154 201 describes a process for the aftertreatment of aluminum oxide layers in a solution which contains an alkali metal silicate and alkaline earth metal cations.
- Calcium or strontium salts are used as alkaline earth metal salts, in particular nitrates or hydroxides used.
- the aqueous solution in the aftertreatment additionally contains at least one complexing agent for alkaline earth metal ions.
- the materials are electrochemically roughened in an aqueous solution containing nitric acid.
- the materials are further anodically oxidized in one or two stages in aqueous solutions containing H 2 SO 4 and / or H 3 PO 4 .
- the aftertreatment is carried out electrochemically or by immersion treatment.
- the object of the invention is therefore to improve a process for the aftertreatment of flat aluminum layer supports which have an aluminum oxide layer in such a way that the degradation of the oxide layer by the silicating can be avoided or at least kept very slight.
- This object is achieved according to the invention by a process of the type described in the introduction that a) the aftertreatment is carried out in an aqueous solution of the ⁇ modification of sodium phyllosilicate Na 2 Si 2 O 5 and b) subsequently rinsed with water containing alkali metal or alkaline earth metal ions being, the Alkali or alkaline earth metal ions can be selected from the group Ca, Mg, Na, K, Sr.
- the SiO 2 / Na 2 O molar ratio of the crystalline layered sodium silicate is preferably in the range from 1.9 to 3.5 to 1.
- the solution in the after-treatment stage a) contains 0.1 to 10% by weight. % of ⁇ -Na 2 Si 2 O 5 .
- the aftertreatment can be carried out as an immersion treatment or else electrochemically, the latter procedure bringing about a certain increase in the alkali resistance and / or improvement in the adsorption behavior of the material. It is assumed that a firmly adhering silicate top layer forms in the pores of the aluminum oxide layer, which protects the aluminum oxide from attacks, the surface topography previously generated, such as roughness and oxide pores, being changed practically or only insignificantly.
- the post-treatment stage a) is carried out electrochemically and / or by an immersion treatment for a time of 10 to 120 seconds and at a temperature of 40 ° C. to 80 ° C.
- the electrochemical aftertreatment is carried out in particular with direct or alternating current, trapezoidal, rectangular or triangular current or overlapping forms of these types of current.
- the current density is generally 0.1 to 10 A / dm 2 and / or the voltage is 3 to 100 volts.
- Post-treatment stage b) with ionic Water generally follows an immersion treatment in a 0.1 to 10% by weight salt solution, this salt solution containing, for example, individually or in combination NaF, NaHCO 3 , CaSO 4 , polyvinyl phosphoric acid and MgSO 4 .
- suitable base materials for the layer supports are also alloys of aluminum which, for example, have a content of more than 98.5% by weight of Al and proportions of Si, Fe, Ti, Cu and Zn.
- All process stages can be carried out discontinuously with plates or foils, but they are preferably carried out continuously with belts in belt systems.
- FIG. 1 shows the structure of layered sodium silicate, which is a pure sodium silicate, ie it is composed exclusively of sodium, silicon and oxygen. It is the ⁇ phase of the crystalline disilicate Na 2 Si 2 O 5 . It is similar to the common water glass, but is anhydrous and crystalline.
- the structure shown in FIG. 1 was determined by X-ray diffraction on single crystals. It shows the polymeric wavy layer structure of the silicate framework made of sodium ions, which are represented in the figure by large bright spheres, oxygen by large black spheres and silicon by small black spheres. The sodium ions are almost in one plane.
- the crystalline layered sodium silicate which is a layered silica, has a SiO 2 / Na 2 O molar ratio of 1.9 to 3.5 to 1.
- the structure of this compound is almost identical to that of the mineral natrosilite, in which it is a ⁇ modification of Na 2 Si 2 O 5 .
- Very pure sand and soda or sodium hydroxide solution are used as the base material in the production of layered sodium silicate, from which a water glass solution is produced. This solution is then dewatered and crystallized at high temperature into the delta modification of the disilicate.
- the product obtained can be ground and, if necessary, compacted into granules. In aqueous solution, water penetrates between two layers and widens the distance.
- the sodium ions can then be exchanged with other ions.
- the calcium and magnesium ions of the rinse water for example tap water, are bound by the crystalline layered silicate in an ion exchange process, ie the sodium ions of the layered silicate are quickly replaced, thereby stabilizing the silicate structure.
- This exchange process takes place faster than the dissolution of the layered sodium silicate - with the effect that the particles are much smaller than when the amorphous silicate.
- the layered sodium silicate provides the desired alkalinity and stabilizes the pH. Hoechst AG offers the product as a builder or builder for detergents.
- layer silicates SKS systems from Hoechst AG, corresponding to S chicht k iesel s äure
- SKS-6 the most important with regard to builder properties in detergents (binding capacity of Mg, Ca ions); it is also advantageously water-soluble for silicating and processing.
- trioctahedral layered silicates such as SKS 20 (mineralogical name “Saponit”) and SKS 21 (“Hectorite”), have water solubility and a good cation exchange capacity of the intermediate Na ions.
- anhydrous layered Na silicate with Kanemite structure (SKS-9) and the synthetic Kanemite (SKS 10) have a very good Ca binding capacity.
- Radiation-sensitive coatings are applied to the aftertreated layer supports, and the offset printing plates thus obtained are converted into the desired printing form in a known manner by imagewise exposure and washing out of the non-image areas with a developer, preferably an aqueous developer solution.
- a developer preferably an aqueous developer solution.
- offset printing plates stand out, their layer support materials using the two-stage process were treated compared to those plates in which the same layer support material was aftertreated with aqueous solutions containing silicates, such as water glass or ⁇ - or ⁇ -Na 2 Si 2 O 5 , by improved alkali resistance, a lower tendency to form color and great resistance to a rubber coating of the offset printing plate.
- a defined area of 7.5 cm x 7.5 cm at room temperature is immersed in a 0.1 N NaOH solution with an electrolyte concentration of 4 g NaOH per liter of fully deionized water and the alkali resistance is determined electrochemically .
- the time course of the potential of an Al / Al 3+ half cell against a reference electrode is measured without current.
- the potential curve provides information about the resistance that the aluminum oxide layer opposes to its dissolution.
- the time in seconds which is determined in the voltage-time diagram after passing through a minimum until a maximum occurs, serves as a measure of the alkali resistance.
- An average value is formed from the measured values of two samples.
- the alkali resistance with an oxide weight of 3.21 g / m 2 is 112 ⁇ 10 seconds, this value being an average of 5 double measurements.
- FIG. 2 shows the silicatization or the covering with silicate on an aluminum surface of a printing plate, in which the aftertreatment with layered sodium silicate of different concentrations in aqueous solution takes place at an immersion bath temperature of 60 ° C. for different lengths of time.
- the surface silicatization is investigated according to the ESCA method, which is "Electron Spectroscopy for Chemical Analyzes", with which the atomic layers on a surface up to approx. 5 nm thick, due to their binding energy position and the intensity of the peak values, the surface atoms, if applicable theirs Binding state, can be determined. Furthermore, the intensity ratio of the different peak values compared to the peak value of aluminum allows an assessment of the atomic occupancy on the aluminum oxide surface.
- FIG. 2 shows the Si / Al and the Na / Al ratio or the coating with Si and Na on the aluminum oxide surface.
- the support with the highest Si / Al ratio is rinsed with fully deionized water and dried and then gummed with an aqueous solution of dextrin, H 3 PO 4 , glycerin, which has a pH of 5.0, and after 16 hours Washed off with fully deionized water.
- the Si / Al ratio does not change after this procedure and is 0.56, and the Na / Al ratio goes to 0.07 back.
- the silication with layered sodium silicate is not attacked by the rubber coating, ie the silicate coating is not removed. Phosphorus from the rubber coating can only be detected in the ESCA spectrum, which is proof that the rubber coating does not attack the silicate coating.
- the silicatisation of the aluminum oxide surface increases with increasing concentration of the layered sodium silicate in the aftertreatment solution, with increasing temperature of the immersion bath (see FIG. 5) and with a longer immersion time. This is expressed in particular in an increase in the Si / Al ratio.
- the concentration of the layered sodium silicate was increased from 1 g / l to 10 g / l of fully deionized water, furthermore demineralized water, the immersion temperature of the aftertreatment solution was raised from 60 to 80 ° C. (see FIG. 5) and the immersion time was 10 s increased to 120 s.
- the ESCA measurements show that the applied layered sodium silicate retains its ion exchange capacity, ie when sodium is rinsed with tap or city water, the sodium ions are exchanged for calcium ions.
- the sodium ions are exchanged for calcium ions.
- the magnesium content after such a rinse is poor due to its peak value
- the exchange of sodium for strontium could also be determined using a strontium solution (see also Table 2).
- Figure 3 shows the oxide degradation in the aluminum oxide layer of a layer or printing plate support.
- the substrate is roughened electrochemically in hydrochloric acid and anodized in sulfuric acid. Its total thickness is 0.3 mm, the oxide weight is 3.21 g / m 2 , the thickness of the oxide layer is about 1 ⁇ m.
- the aftertreatment is carried out in accordance with the process according to the invention in an aqueous solution with a 1% concentration of the layered sodium silicate, deionized water being used. The solution had a pH of 11.4.
- the printing plate carrier was immersed in the immersion bath at a temperature of 60 ° C. The diving times were 10 to 120 s. As can be seen from Figure 3, the aluminum oxide is attacked only slightly.
- the surfaces of the substrate which were treated for 10 s, 30 s, and 120 s in the 1% sodium layer silicate solution at 60 ° C, show little change in SEM images compared to the starting material, only that Porosity of the surface, ie the refinement of the pore structure increases slightly.
- the surfaces of substrates were also investigated, in which sodium metasilicates Na 2 SiO 3 x 5 H 2 O were used for the silicatization, under otherwise identical immersion conditions. These investigations were carried out for the diving temperatures of 25 ° C and 60 ° C. A very strong oxide degradation is found, which is still at a low diving temperature of 25 ° C is significantly higher than when silicating with layered sodium silicate.
- the 1% sodium metasilicate solution (10 g / l Na 2 SiO 3 x 5 H 2 O, whereby the water of crystallization is not taken into account) has a pH of 12.2.
- the oxide degradation is determined gravimetrically in a chrome / phosphoric acid bath at a higher temperature of approx. 70 ° C by differential weighing; the starting oxide weight of the support is 3.21 g / m 2 at an immersion temperature of 60 ° C.
- the basis weight of aluminum oxide layers is determined by chemical detachment in accordance with DIN standard 30944 (March 1969 edition) in conjunction with an internal operating regulation of the applicant from 1973.
- rinsing with demineralized water at most provides a slightly increased alkali resistance, which is only slightly dependent on the immersion temperature.
- the aftertreatment with city water results in an alkali resistance of the oxidized aluminum surface, which is significantly higher than with the aftertreatment with demineralized water. This resistance to alkali rises sharply with increasing immersion bath temperature of the layered sodium silicate solution.
- Alkali resistance values were determined for the following rinse solutions: Rinse solutions: Alkali resistance: 0.4% NaHCO 3 in VE-H 2 O 210/204 s to the maximum 1.0% NaHCO 3 in VE-H 2 O 350 " 0.4% Na 2 CO 3 in VE-H 2 O 258 " 0.4% Na 2 SiO 3 in VE-H 2 O 413 " 0.4% Na 3 PO 4 in VE-H 2 O 278 " , PO 4 3-, SiO 3 2-, CO 3 2- anions can be significantly enhanced by rinsing with the appropriate salt solutions - in addition to the alkaline earth metal cations and anions decisive influence on the size of the alkali resistance, for example, by HCO 3 have.
- the table also shows that in the case of a rinsing solution in NaHCO 3 , the alkali resistance also increases with increasing concentration.
- Table 2 shows alkali resistance values for further rinsing solutions, together with the X / Al ratios of various alkaline earth metals X in the rinsing solutions to aluminum Al, measured by the ESCA method.
- the samples were prepared as standard, that is, siliconized with 1% sodium phyllosilicate solution in demineralized water, at an immersion temperature of 60 ° C and an immersion time of 120 s. It was rinsed with demineralized water and with solutions in which 0.4% strength CaCl 2 , MgCl 2 , SrCl 2 and dextrin were dissolved. Further Solutions were CaSO 4 , Na 2 SO 4 , MgSO 4 , NaF, polyvinyl phosphoric acid NaHCO 3 . After drying, the alkali resistance value and the X / Al ratios were determined by ESCA measurements in order to determine the surface coverage by Si, Na, Ca, Sr and the like.
- X / Al X Ca, Mg, Sr, F, P Si / Al Well / Al X / Al default VE water 80-120 0.46 0.20 - " 0.4% igCaCl 2 / VE 145 0.47 0.02 0.07 / approx " "MgCl 2 / VE 118 0.48 0.04 ?
- FIGS. 5 and 6 The results on the temperature dependence of the silication are shown in FIGS. 5 and 6: According to FIG. 5, the Si / Al ratio is independent of the rinsing and increases sharply with increasing temperature and with increasing immersion time.
- the layered sodium silicate on the Al / AlOOH surface largely retains its ion exchange function; the alkaline earth ions replace the Na ions in the silicated Al / AlOOH surface.
- layered substrates of type P51 in the 32 x 27 cm format which were coated with sodium silicate and rinsed with city water, were produced as standard and hand-coated with a positive printing plate formulation (P61 solution) and a negative printing plate formulation (N50 solution).
- P61 solution positive printing plate formulation
- N50 solution negative printing plate formulation
- an untreated P51 substrate which was also not treated with polyvinylphosphonic acid solution, was coated with the same printing plate formulations and then dried.
- the positive layer supports P51 were developed for 60 s with an EP26 developer and then consumed.
- the negative layer supports N50 were treated by hand with 30 ml of DN-5 developer for 60 s without exposure and then brewed.
- the essential components of the EP-26 developer are Na silicate, hydroxide, tetraborate, Sr levolinate, polyglycol and water.
- the DN-5 developer contains benzyl alcohol, mono-, di- and triethanolamine, nitrogen and has a pH of 10.9.
- the formation of blue haze is more pronounced in the case of the positive layer supports than the formation of green haze in the case of the negative layer supports, the fog formation being the least noticeable on the layer supports in which the silicate coating has been rinsed with city water.
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Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4417907 | 1994-05-21 | ||
DE4417907A DE4417907A1 (de) | 1994-05-21 | 1994-05-21 | Verfahren zur Nachbehandlung von platten-, folien- oder bandförmigem Material, Träger aus derartigem Material und seine Verwendung für Offsetdruckplatten |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0683248A1 EP0683248A1 (de) | 1995-11-22 |
EP0683248B1 true EP0683248B1 (de) | 1997-12-17 |
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ID=6518714
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP95107331A Expired - Lifetime EP0683248B1 (de) | 1994-05-21 | 1995-05-15 | Verfahren zur Nachbehandlung von platten-, folien- oder bandförmigem Material, Träger aus derartigem Material und seine Verwendung für Offsetdruckplatten |
Country Status (7)
Country | Link |
---|---|
US (2) | US5556531A (ko) |
EP (1) | EP0683248B1 (ko) |
JP (1) | JPH07316882A (ko) |
KR (1) | KR950032719A (ko) |
AT (1) | ATE161297T1 (ko) |
BR (1) | BR9502487A (ko) |
DE (2) | DE4417907A1 (ko) |
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JP3830114B2 (ja) * | 1997-09-29 | 2006-10-04 | 富士写真フイルム株式会社 | ポジ型感光性平版印刷版 |
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JP5813063B2 (ja) | 2012-07-27 | 2015-11-17 | 富士フイルム株式会社 | 平版印刷版用支持体およびその製造方法、並びに、平版印刷版原版 |
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Publication number | Priority date | Publication date | Assignee | Title |
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US2882153A (en) * | 1954-02-04 | 1959-04-14 | Polychrome Corp | Planographic printing plate |
US2882152A (en) * | 1957-06-21 | 1959-04-14 | Malon H Dickerson | High speed developers |
US3902976A (en) * | 1974-10-01 | 1975-09-02 | S O Litho Corp | Corrosion and abrasion resistant aluminum and aluminum alloy plates particularly useful as support members for photolithographic plates and the like |
DE3232485A1 (de) * | 1982-09-01 | 1984-03-01 | Hoechst Ag, 6230 Frankfurt | Verfahren zur nachbehandlung von aluminiumoxidschichten mit alkalisilikat enthaltenden waessrigen loesungen und dessen verwendung bei der herstellung von offsetdruckplattentraegern |
DE3406102A1 (de) * | 1984-02-21 | 1985-08-22 | Hoechst Ag, 6230 Frankfurt | Verfahren zur nachbehandlung von aluminiumoxidschichten mit alkalimetallsilikat enthaltenden waessrigen loesungen und deren verwendung bei der herstellung von offsetdruckplattentraegern |
-
1994
- 1994-05-21 DE DE4417907A patent/DE4417907A1/de not_active Withdrawn
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1995
- 1995-05-05 US US08/435,162 patent/US5556531A/en not_active Expired - Fee Related
- 1995-05-15 AT AT95107331T patent/ATE161297T1/de active
- 1995-05-15 EP EP95107331A patent/EP0683248B1/de not_active Expired - Lifetime
- 1995-05-15 DE DE59501119T patent/DE59501119D1/de not_active Expired - Fee Related
- 1995-05-19 BR BR9502487A patent/BR9502487A/pt not_active Application Discontinuation
- 1995-05-20 KR KR1019950012654A patent/KR950032719A/ko not_active Application Discontinuation
- 1995-05-22 JP JP7122305A patent/JPH07316882A/ja active Pending
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1996
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US5770315A (en) | 1998-06-23 |
US5556531A (en) | 1996-09-17 |
JPH07316882A (ja) | 1995-12-05 |
EP0683248A1 (de) | 1995-11-22 |
BR9502487A (pt) | 1995-12-19 |
ATE161297T1 (de) | 1998-01-15 |
KR950032719A (ko) | 1995-12-22 |
DE59501119D1 (de) | 1998-01-29 |
DE4417907A1 (de) | 1995-11-23 |
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