EP0190643B1 - Matériau de supports hydrophilisés pour plaques d'impression offset, procédé de fabrication et leur emploi - Google Patents

Matériau de supports hydrophilisés pour plaques d'impression offset, procédé de fabrication et leur emploi Download PDF

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Publication number
EP0190643B1
EP0190643B1 EP86101090A EP86101090A EP0190643B1 EP 0190643 B1 EP0190643 B1 EP 0190643B1 EP 86101090 A EP86101090 A EP 86101090A EP 86101090 A EP86101090 A EP 86101090A EP 0190643 B1 EP0190643 B1 EP 0190643B1
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EP
European Patent Office
Prior art keywords
aluminum
support material
acid
coating
und
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 - Lifetime
Application number
EP86101090A
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German (de)
English (en)
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EP0190643A2 (fr
EP0190643A3 (en
Inventor
Michael Dr. Dipl.-Chem. Brenk
Renate Ernst
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Hoechst AG
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Hoechst AG
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Publication of EP0190643A3 publication Critical patent/EP0190643A3/de
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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
    • 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 plate, film or ribbon-shaped carrier materials for offset printing plates based on aluminum with a hydrophilic coating, a process for the production of these materials and the use of the materials in the production of offset printing plates.
  • Carrier materials for offset printing plates are either directly from the consumer or. provided by the manufacturer of pre-coated printing plates on one or both sides with a light-sensitive layer (copying layer), with the help of which a printing image is generated in a photomechanical way. After the printing image has been produced, the support carries the printing image areas and at the same time forms the hydrophilic background for the lithographic printing process in the non-image areas (non-image areas).
  • Aluminum, steel, copper, brass or zinc, but also plastic films or paper can be used as the base material for such layers. These raw materials are processed through suitable operations such as e.g. Grain, matt chrome plating, surface oxidation and / or application of an intermediate layer are converted into layer supports for offset printing plates.
  • Aluminum, which is probably the most frequently used base material for offset printing plates today, is roughened on the surface by known methods by dry brushing, wet brushing, sandblasting, chemical and / or electrochemical treatment. In order to increase the abrasion resistance, the roughened substrate can also be subjected to an anodization step to build up a thin oxide layer.
  • the support materials in particular anodically oxidized support materials based on aluminum, are often subjected to a further treatment step to improve the layer adhesion, to increase the hydrophilicity and / or to facilitate the developability of the light-sensitive layers before the application of a light-sensitive layer for example the following methods:
  • the use of salts of these compounds is also mentioned, but is not specified in detail.
  • DE-B 10 56 931 describes the use of water-soluble, linear copolymers based on alkyl vinyl ethers and maleic anhydrides in light-sensitive layers for printing plates.
  • these copolymers those in which the maleic anhydride component has not been reacted with, or more or less completely, with ammonia, an alkali metal hydroxide or an alcohol are particularly hydrophilic.
  • DE-B 10 91 433 discloses the hydrophilization of printing plate support materials based on metals with film-forming organic polymers such as polymethacrylic acid or sodium carboxymethyl cellulose or hydroxyethyl cellulose in the case of aluminum supports or a mixed polymer of methyl vinyl ether and maleic anhydride in the case of magnesium supports.
  • film-forming organic polymers such as polymethacrylic acid or sodium carboxymethyl cellulose or hydroxyethyl cellulose in the case of aluminum supports or a mixed polymer of methyl vinyl ether and maleic anhydride in the case of magnesium supports.
  • water-soluble polyfunctional amino-urea-aldehyde synthetic resins or sulfonated urea-aldehyde synthetic resins are first used, which are in a water-insoluble state on the metal support be cured.
  • the hydrophilic layer on a printing plate support material according to DE-C 21 07 901 is formed from a water-insoluble hydrophilic acrylate or methacrylate homopolymer or copolymer with a water absorption of at least 20% by weight.
  • the layer weight of the hydrophilic adhesive layer on cellulose ether is 0.2 to 1.1 mg / dm 2 , and the same layer weight is also given for the water-soluble salts.
  • the mixture of cellulose ether and salt is applied to the support in aqueous solution, optionally with the addition of an organic solvent and / or a surfactant.
  • hydrophilizing agents for printing plate support materials according to US Pat. No. 4,049,746 contain salt-like reaction products of water-soluble polyacrylic resins with carboxyl groups and polyalkyleneimine-urea-aldehyde resins.
  • GB-A 1 246 696 describes hydrophilic colloids such as hydroxyethyl cellulose, polyacrylamide, polyethylene oxide, polyvinyl pyrrolidone, starch or gum arabic as hydrophilizing agents for anodized aluminum printing plate supports.
  • US Pat. No. 4,214,531 uses a process for treating image-bearing offset printing plates with polyacrylamide or a mixture of polyacrylamide and polyacrylic acid.
  • SU-A 647 142 uses a copolymer of acrylamide and vinyl monomers for the hydrophilization of offset printing plates.
  • DE-C 10 91 433 describes a process for the aftertreatment of offset printing plate supports with polymers of methacrylic acid, methyl vinyl ether and maleic anhydride.
  • DE-A 29 47 708 describes u.a. Ni salt solutions of acrylamide and acrylic acid as well as acrylamide and vinyl pyrrolidone.
  • the object of the invention is therefore to produce support materials for offset printing plates with good hydrophilization properties that they are equally suitable as supports for positive, negative or electrophotographic photosensitive layers without reducing the shelf life, reactions between the hydrophilizing agent and the photosensitive layer occur or that Shift liability is reduced.
  • the invention is based on a plate, film or tape-shaped carrier material for offset printing plates consisting of optionally pretreated aluminum or one of its alloys, which has a hydrophilic coating of a phosphonic acid compound on at least one side.
  • the hydrophilic coating consists of a) a polymer of acrylamidoisobutylenephosphonic acid or b) a copolymer of acrylamide and acrylamidoisobutylenephosphonic acid or c) a salt of a) or b) with at least one divalent metal cation.
  • the metal cations are generally used in the form of their salts with mineral acid anions or as acetates; the divalent, trivalent or tetravalent, in particular the divalent, are preferred.
  • the cations are in particular V 5 + - , Bis + -, A13 + -, Fe3 + - , Zr4 + - , Sn4 + - , Ca2 + -, Ba2 + - , Sr 2 + - , T J3 + -, Co2 + - , Fe2 + - , Mn2 + -, Ni2 + -, Cu2 + - , Zn2 + - or Mg 2 + - ions.
  • reaction products can be prepared in a simple manner in aqueous solution at temperatures from 20 to 100 ° C., preferably at 25 to 40 ° C.
  • the metal salt is slowly added dropwise to the aqueous polymer solution, dissolved in water or, if necessary, dissolved in dilute mineral acid. This leads to the immediate conversion of the reaction components to the previously described products.
  • the rapid onset of reaction is shown - depending on the metal cation used - in the immediately changing color of the solution or through the formation of precipitation.
  • the products can be precipitated by neutralizing the reaction solution with dilute alkali hydroxide or ammonia solutions, the unreacted starting products remaining in the solution.
  • the yields of these reactions are over 90%.
  • the acid forms of the polymers described it is also possible to use their salt forms with a monovalent cation such as sodium or ammonium salt.
  • the aqueous solutions of the copolymers are used in concentrations of 0.02 to 5%, preferably in concentrations of 0.1 to 1%.
  • the isolated and dried reaction products are preferably in 0.1 to 10%, in particular 0.5 to 3%, mineral acids, preferably phosphoric acid, in concentrations of 0, 05 to 5%, especially in concentrations of 0.1 to 1%, dissolved.
  • the treatment of these substrates with the solutions is expediently carried out by dipping formats or by passing the substrate tape through a bath of these solutions. Temperatures of 20 to 95 ° C., preferably of 25 to 60 ° C. and residence times of 2 seconds to 10 minutes, preferably of 10 seconds to 3 minutes, are found to be the most favorable for practical use. An increase in the bath temperature accelerates the chemisorption of the copolymers and the polymer-metal complexes on the substrate. This makes it possible to reduce the dwell times considerably, particularly in the case of continuous strip treatment.
  • the immersion treatment is then advantageously followed by a rinsing step with water. The thus treated substrate is then advantageously dried at of 110 to 130 ° C.
  • the treatment of the aluminum substrate with the salts of the copolymers can also be carried out as a two-stage process.
  • the substrate is immersed, for example, in a 0.01 to 10%, preferably 0.1 to 5%, aqueous solution of the starting polymer.
  • the substrate can then be transferred without prior rinsing or drying into a second bath which contains a 0.1% to saturated, preferably 0.5 to 10% aqueous salt solution with the polyvalent metal ions listed above.
  • the rinsing and drying is carried out as in the one-step process.
  • the reaction products described above are formed on the substrate during the treatment.
  • This process variant can also be used to apply the reaction products of trivalent metal ions, which are sparingly soluble in strongly acidic media, to the substrate.
  • the support materials according to the invention thus produced can then be coated with various light-sensitive layers for the production of offset printing plates.
  • the method according to the invention can also be applied to other aluminum alloys.
  • the aluminum support materials for printing plates which are very common in practice, are generally mechanically (e.g. by brushing and / or with abrasive treatments), chemically (e.g. by etching agents) or electrochemically (e.g. B. roughened by AC treatment in aqueous HCl or ENT solutions).
  • Aluminum printing plates with electrochemical roughening are used in particular for the present invention.
  • the process parameters in the roughening stage are in the following ranges: the temperature of the electrolyte between 20 and 60 ° C, the active substance (acid, salt) concentration between 5 and 100 g / i, the current density between 15 and 130 A / dm 2 , the residence time between 10 and 100 sec and the electrolyte flow rate on the surface of the workpiece to be treated between 5 and 100 cm / sec; AC is usually used as the type of current, but modified types of current such as AC with different amplitudes of the current strength are also possible for the anode and cathode currents.
  • the average roughness depth Rz of the roughened surface is in the range from about 1 to 15 ⁇ m, in particular in the range from 4 to 8 ⁇ m.
  • the roughness depth is determined in accordance with DIN 4768 (as of October 1970), the roughness depth R z is then the arithmetic mean of the individual roughness depths of five adjacent individual measuring sections.
  • the individual roughness depth is defined as the distance between two parallels to the middle line, which touch the roughness profile at the highest or lowest point within the individual measuring sections.
  • the individual measuring section is the fifth part of the length of the part of the roughness profile which is used directly for evaluation and is projected perpendicularly onto the middle line.
  • the middle line is the line parallel to the general direction of the roughness profile from the shape of the geometrically ideal profile, which divides the roughness profile in such a way that the sum of the material-filled areas above it and the material-free areas below it are equal.
  • Direct current is preferably used for anodic oxidation, however alternating current or a combination of these types of current (e.g. direct current with superimposed alternating current) can also be used will.
  • the layer weights of aluminum oxide range from 1 to 10 g / m 2 , corresponding to a layer thickness of about 0.3 to 3.0 (lm.
  • all layers are suitable as light-sensitive layers which, after exposure, optionally with subsequent development and / or fixation, provide an imagewise surface from which printing can take place. They are either applied by the manufacturer of presensitized printing plates or directly by the consumer on one of the usual carrier materials.
  • photo-semiconducting layers such as e.g. in DE-C 11 17 391, 15 22 497.15 72 312, 23 22 046 and 23 22 047 are described, to which carrier materials are applied, which results in highly light-sensitive, electrophotographic layers.
  • the coated offset printing plates obtained from the carrier materials according to the invention are converted into the desired printing form in a known manner by imagewise exposure or irradiation 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, the base carrier materials of which have been treated according to the invention have a significantly lower color haze and improved hydrophilicity compared to plates which have been treated with homopolymeric acrylamide, with polymeric vinylphosphonic acid or only with hot water.
  • the liability of the photosensitive Layer on the surface of the support was better in the samples treated according to the invention than in the comparison samples.
  • a bright rolled aluminum strip (DIN material No. 3.0255) with a thickness of 0.3 mm is degreased with an aqueous alkaline 2% pickling solution at an elevated temperature of about 50 to 70 ° C.
  • the electrochemical roughening of the aluminum surface is carried out with alternating current and in an electrolyte containing ENT; this results in a surface roughness with an Rr value of 6 ⁇ m.
  • the subsequent anodic oxidation is carried out in an electrolyte containing sulfuric acid in accordance with the process described in DE-A 28 11 396; the oxide weight is about 3.0 g / m 2.
  • a carrier produced in this way is designated by the number 1 in Tables 2 and 3.
  • the aluminum strip prepared in this way is then passed through a 60 ° C. bath from a 0.5% solution which contains one of the polymers according to the invention or one of the comparison substances (N1 to NV13).
  • the compositions of these solutions are listed in Table 1.
  • the residence time in the bath is 30 seconds.
  • the excess solution is then removed with tap water in a rinsing step and the strip is dried with hot air at temperatures between 100 and 130 ° C.
  • A2 A bright rolled aluminum strip (DIN material no. 3.0515) with a thickness of 0.3 mm is degreased with an aqueous alkaline 2% pickling solution at an elevated temperature of around 50 to 70 ° C.
  • the electrochemical roughening of the aluminum surface takes place with alternating current and in an electrolyte containing hydrochloric acid; a surface roughness with an Rz value of 6 11 m is obtained.
  • the subsequent anodic oxidation is carried out in an electrolyte containing sulfuric acid in accordance with the process described in DE-A 28 11 396; the oxide weight is about 3.0 g / m 2 .
  • a carrier produced in this way is designated in Table 2 and 3 with the number 2.
  • the aluminum strip prepared in this way is then passed through a 50 ° C. bath from a 0.5% solution which contains one of the polymers according to the invention or one of the comparison substances (N1 to NV13).
  • the compositions of these solutions are listed in Table 1.
  • a carrier produced in this way is designated by the number 3 in Tables 2 and 3.
  • the carriers prepared in this way are immersed in a 60 ° C. bath of an aqueous solution of 0.4% of one of the polymers listed in Table 1 under N1 to NV13.
  • the residence time in the bath is 60 seconds.
  • the excess solution is then removed with deionized water in a rinsing step and the carrier is air-dried.
  • Carriers from Example A2 are immersed in a 0.2% solution of preparations N1 to NV12 (Table 1) at 40 ° C.
  • the carriers are switched as an anode and treated with direct current at 10 V for 20 seconds.
  • the current drops from initially 3 A / dm 2 to 0.2 A / dm 2 during this treatment.
  • the excess solution is then removed with deionized water in a rinsing step and the supports are air-dried.
  • Table 3 lists the carriers thus produced and the results of the measurements described below.
  • the measure of the alkali resistance of an aluminum oxide layer is the dissolution rate of the layer in seconds in an alkaline zincate solution.
  • 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 500 ml of distilled H 2 O, 480 g of KOH and 80 g of zinc oxide is placed on the surface to be examined and the period of time until the appearance of metallic zinc is determined, which can be recognized by the blackening of the examination site. This "zinc certificate" is mentioned in column 4 of Table 2.
  • the test is carried out using wetting angle measurements against a drop of water.
  • the angle is determined between the carrier surface and a tangent placed through the point of contact of the drop; it is generally between 0 ° and 90 ° .
  • the information in column 5 of Table 2 relates to these contact angle measurements.
  • the carriers are dried as described under 3.
  • the carriers are dried as described under 3.
  • the plate is then rinsed off with a powerful jet of water, removing the areas of the photoconductor layer which are not covered with toner.
  • the plate is then ready for printing.
  • the non-image areas of the plate show good hydrophilicity and show no signs of attack even after exposure to alkaline solutions. Several tens of thousands of good prints can be achieved with the printing form.
  • Table 2 shows that the products according to the invention are better than the prior art in many properties, but not worse in none.
  • Table 3 shows that the electrochemically aftertreated supports have correspondingly good values as in Table 2, the values for the zincate test in particular being still improved.
  • supports which had been prepared according to Examples 1 to 3 of Table 2, as described under D1 were coated with a positive-working photosensitive layer and printing forms were produced by exposure and development. With this, printing tests were undertaken which delivered up to 210,000 perfect prints.
  • a printing form which was produced analogously with a carrier of comparative example NV12 (Table 2) showed poorer freewheeling behavior. After 170,000 prints, fine halftone dots were no longer reproduced correctly.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Printing Plates And Materials Therefor (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Claims (14)

1. Matériau de support sous forme de plaques, feuilles ou bandes pour plaques d'impression offset, constitué d'aluminium éventuellement prétraité ou d'un de ses alliages, qui présente, sur au moins une face, un revêtement hydrophile en un composé d'acide phosphonique, caractérisé en ce que le revêtement hydrophile se compose de
a) un polymère de l'acide acrylamidoisobutylènephosphonique ou
b) un copolymère d'acrylamide et de l'acide acrylamidoisobutylènephosphonique ou
c) un sel de a) ou b) avec un cation métallique au moins divalent.
2. Matériau de support selon la revendication 1, caractérisé en ce que le rapport en monomères de l'acrylamide et de l'acide acrylamidoisobutylènephosphonique des copolymères de b) ou c) est de 1:99 à 99:1.
3. Matériau de support selon la revendication 2, caractérisé en ce que le rapport en monomères est de 3:97 à 90:10.
4. Matériau de support selon l'une quelconque des revendications 1 à 3, caractérisé en ce que le cation métallique du revêtement c) est V5+, Bi3+, AI3+, Fe3+, Zr4+, Sn4+, Ca2+, Ba2+, Sr2+, Ti3+, Co2+, Fe2+, Mn2+, Ni2+, Cu2+, Zn2+, ou Mg2+.
5. Matériau de support selon l'une quelconque des revendications 1 à 4, caractérisé en ce que le revêtement se compose de mélanges des produits a) et/ou b) et/ou c).
6. Matériau de support selon l'une quelconque des revendications 1 à 5, caractérisé en ce que l'aluminium est décapé.
7. Matériau de support selon l'une quelconque des revendications 1 à 6, caractérisé en ce que l'aluminium est grainé.
8. Matériau de support selon l'une quelconque des revendications 1 à 7, caractérisé en ce que l'aluminium est oxydé anodiquement.
9. Matériau de support selon l'une quelconque des revendications 6 à 8, caractérisé en ce que l'aluminium présente une pronfondeur de rugosité Rz allant de 3 à 10 µm.
10. Matériau de support selon l'une des revendications 8 ou 9, caractérisé en ce que la couche d'oxyde de l'aluminium va de 0,3 à 3,0 tim.
11. Procédé de fabrication d'un matériau de support pour plaques d'impression offset selon l'une quelconque des revendications 1 à 10, caractérisé en ce que l'on recouvre l'aluminium ou ses alliages avec les produits dissous a) à c) ou leurs mélanges, à une concentration allant de 0,02 à 5,0% en poids dans une solution aqueuse éventuellement acide, par immersion ou traitement électrochimique, et ensuite que l'on sèche la couche formée.
12. Procédé de fabrication d'un matériau de support selon l'une quelconque des revendications 1 à 10, caractérisé en ce que, pour la fabrication d'un revêtement c), on traite l'aluminium ou ses alliages d'abord avec une solution à une concentration allant de 0,01 à 10,0% des polymères a) et/ou b), et ensuite avec une solution, de préférence aqueuse, à une concentration allant de 0,1% à la saturation, d'un sel avec les cations V5+, Bi3+, A13+, Fe3+, Zr4+, Sn4+, Ca2+, Ba2+, Sr2+, Ti3+, Co2+, Fe2+, Mn2+, N12+, Cu2+, Zn2+, ou Mg2+, et que l'on sèche la couche formée à partir des produits de la réaction.
13. Procédé de fabrication d'un matériau de support selon l'une des revendications 11 ou 12, caractérisé en ce que l'on décape et/ou oxyde anodiquement l'aluminium ou ses alliages avant revêtement avec le composé hydrophile et/ou qu'on l'oxyde anodiquement.
14. Utilisation d'un matériau de support selon l'une quelconque des revendications 1 à 10 pour le revêtement avec des substances photosensibles.
EP86101090A 1985-02-08 1986-01-28 Matériau de supports hydrophilisés pour plaques d'impression offset, procédé de fabrication et leur emploi Expired - Lifetime EP0190643B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19853504331 DE3504331A1 (de) 1985-02-08 1985-02-08 Hydrophilierte traegermaterialien fuer offsetdruckplatten, ein verfahren zu ihrer herstellung und ihre verwendung
DE3504331 1985-02-08

Publications (3)

Publication Number Publication Date
EP0190643A2 EP0190643A2 (fr) 1986-08-13
EP0190643A3 EP0190643A3 (en) 1987-10-21
EP0190643B1 true EP0190643B1 (fr) 1990-05-02

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP86101090A Expired - Lifetime EP0190643B1 (fr) 1985-02-08 1986-01-28 Matériau de supports hydrophilisés pour plaques d'impression offset, procédé de fabrication et leur emploi

Country Status (9)

Country Link
EP (1) EP0190643B1 (fr)
JP (1) JPS61182988A (fr)
CN (1) CN1010897B (fr)
AU (1) AU5328086A (fr)
BR (1) BR8600541A (fr)
CA (1) CA1299007C (fr)
DE (2) DE3504331A1 (fr)
ES (1) ES8705981A1 (fr)
ZA (1) ZA86876B (fr)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0790669B2 (ja) * 1986-03-19 1995-10-04 大日本インキ化学工業株式会社 平版印刷版用支持体の製造方法
DE4039920A1 (de) * 1990-12-14 1992-06-17 Basf Ag Neue polyethylenimin- und polyvinylamin-derivate, mit diesen derivaten beschichtete traegermaterialien auf der basis von aluminium sowie deren verwendung zur herstellung von offsetdruckplatten
US5368974A (en) * 1993-05-25 1994-11-29 Eastman Kodak Company Lithographic printing plates having a hydrophilic barrier layer comprised of a copolymer of vinylphosphonic acid and acrylamide overlying an aluminum support
EP0689096B1 (fr) 1994-06-16 1999-09-22 Kodak Polychrome Graphics LLC Plaques d'impression lithographiques utilisant une couche oléophile à formation d'image
DE4423140A1 (de) * 1994-07-01 1996-01-04 Hoechst Ag Hydrophiliertes Trägermaterial und damit hergestelltes Aufzeichnungsmaterial
DE19543934A1 (de) 1995-11-25 1997-05-28 Hoechst Ag Trägermaterial aus Aluminium oder seinen Legierungen, mit einer hydrophilierenden Schicht, und Verfahren zur Herstellung des Trägermaterials
WO1997020698A1 (fr) * 1995-12-01 1997-06-12 Toyo Boseki Kabushiki Kaisha Substrat stratifie, nouvelle plaque utilisant le substrat pour une impression photolithographique et pour une impression lithographique directe
GB9726994D0 (en) * 1997-12-23 1998-02-18 Ici Plc Polymeric film
CZ20011605A3 (cs) * 1998-10-15 2002-02-13 Henkel Corporation Hydrofilizační činidlo kovového materiálu, hydrofilizační tekutina, způsob hydrofilizace, kovový materiál a tepelný výměník
KR101344792B1 (ko) * 2010-12-17 2013-12-24 제일모직주식회사 하드마스크 조성물, 이를 사용한 패턴 형성 방법 및 상기 패턴을 포함하는 반도체 집적회로 디바이스

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Publication number Priority date Publication date Assignee Title
DE3126626A1 (de) * 1981-07-06 1983-01-20 Hoechst Ag, 6000 Frankfurt Hydrophilierte traegermaterialien fuer offsetdruckplatten, ein verfahren zu ihrer herstellung und ihre verwendung
DE3126636A1 (de) * 1981-07-06 1983-01-27 Hoechst Ag, 6000 Frankfurt Hydrophilierte traegermaterialien fuer offsetdruckplatten, ein verfahren zu ihrer herstellung und ihre verwendung

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Publication number Publication date
ZA86876B (en) 1986-09-24
EP0190643A2 (fr) 1986-08-13
DE3504331A1 (de) 1986-08-14
CA1299007C (fr) 1992-04-21
ES551694A0 (es) 1987-05-16
BR8600541A (pt) 1986-10-21
JPS61182988A (ja) 1986-08-15
EP0190643A3 (en) 1987-10-21
ES8705981A1 (es) 1987-05-16
CN86101022A (zh) 1986-08-06
CN1010897B (zh) 1990-12-19
DE3670804D1 (de) 1990-06-07
AU5328086A (en) 1986-08-14

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