EP0052968B1 - Revêtement de substrats polymériques - Google Patents

Revêtement de substrats polymériques Download PDF

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Publication number
EP0052968B1
EP0052968B1 EP19810305262 EP81305262A EP0052968B1 EP 0052968 B1 EP0052968 B1 EP 0052968B1 EP 19810305262 EP19810305262 EP 19810305262 EP 81305262 A EP81305262 A EP 81305262A EP 0052968 B1 EP0052968 B1 EP 0052968B1
Authority
EP
European Patent Office
Prior art keywords
reactant
process according
surface layer
polymeric material
reactant comprises
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
EP19810305262
Other languages
German (de)
English (en)
Other versions
EP0052968A2 (fr
EP0052968A3 (en
Inventor
Phillip Rodney Kellner
Rexwell Barry Nicholls
Mohammed Aslam Sahi
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.)
Crosfield Electronics Ltd
Original Assignee
Crosfield Electronics Ltd
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 Crosfield Electronics Ltd filed Critical Crosfield Electronics Ltd
Publication of EP0052968A2 publication Critical patent/EP0052968A2/fr
Publication of EP0052968A3 publication Critical patent/EP0052968A3/en
Application granted granted Critical
Publication of EP0052968B1 publication Critical patent/EP0052968B1/fr
Expired legal-status Critical Current

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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
    • B41N3/003—Preparing for use and conserving printing surfaces of intaglio formes, e.g. application of a wear-resistant coating, such as chrome, on the already-engraved plate or cylinder; Preparing for reuse, e.g. removing of the Ballard shell; Correction of the engraving
    • 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
    • B41N1/12—Printing plates or foils; Materials therefor non-metallic other than stone, e.g. printing plates or foils comprising inorganic materials in an organic matrix

Definitions

  • the layer that is applied should conform accurately and bond firmly to the polymeric surface and that it should not blister away from the surface during use.
  • a protective layer over a substrate. If the protective layer tends to be incompatible with the substrate it is common practice to apply an organic liquid to the surface of the substrate, before the protective layer, so as to dissolve or swell the substrate with the intention of improving adhesion of the protective layer to it. The dissolution or swelling that occurs is on a gross scale and is generally visible to the naked eye.
  • a process is known in which a surface layer of an epoxy resin plate is prepared to receive an adherent coating by application of a reactant, said process comprising treating the surface layer only with a 50 vol.% N-methyl-2-pyrrolidone solution in 2-butoxy-ethanol and then with chromic acid. An adherent coating is subsequently applied to the treated surface by electroless metal deposition.
  • the treatment with the N-methyl-2-pyrrolidone solution is performed at 21-54°C during 0.5-15 minutes preferably 3-5 minutes.
  • the known processes concern the preparation of printed circuits on an epoxy resin plate.
  • the preparation of an intaglio printing member is not disclosed.
  • an intaglio print member having a surface layer that is formed of polymeric material and that is engraved with intaglio cells and that has substantially non-print characteristics between the cells is prepared to receive an adherent coating by a process comprising penetrating the surface layer only with a first reactant and then with a second reactant and causing or allowing the second reactant to react with the first reactant within the surface layer to form pits that extend from the surface into the surface layer substantially without chemical degradation of the polymeric material between the pits.
  • the prepared surface then has an appropriate hard wearing, adherent coating applied to it.
  • the coating is a metal coating for instance of copper, nickel or chromium, and is preferably applied in an electroless manner.
  • plating may be conducted by depositing a colloidal palladium based solution, preferably after altering the charge on the surface by subjecting it to a cationic surfactant solution, followed by electroless deposition of copper, nickel, or chromium in conventional manner. Suitable plating methods are described in British Patent Specification No. 1,524,717.
  • the gravure cells in the polymeric layer may be discrete cells or, when the surface is a cylinder, may be a continuous spiral and may be at least 15 microns deep.
  • This engraving is preferably carried out using an electron, ion or laser beam.
  • the polymeric material is preferably of a composition that, when struck by an electron, ion or laser beam in an area, is converted to volatile products and volatilises throughout the entire area while remaining as a rigid solid in the zone adjacent the area where it volatilises, as described in our British Patent Specification No. 2034636.
  • the epoxy or other polymeric material includes carbon black and will generally have been mechanically polished, for example by diamond turning, before engraving so as to give it non-print characteristics before being engraved, i.e. between the engraved cells.
  • Other polymeric materials that may be prepared in accordance with the invention for subsequent coating with metal or other coatings include, for instance, polypropylene.
  • the first reactant for this may consist solely of one of the specified pyrrole derivatives and then the second reactant may be chromic acid or a chromic acid-sulphuric acid mixture.
  • first and second reactants react to form pits that extend to the surface it is possible in the invention to avoid the disadvantages of trapping within the surface layer substantial quantities of a swelling or softening agent. Since the reaction occurs primarily with the first reactant, with the polymeric material between reaction sites being left substantially undegraded, it is possible in the invention to avoid the formation of a surface layer contaminated with large amounts of degraded polymeric material.
  • the first reactant preferably comprises an organic solvent and penetrates the surface layer during the process substantially without swelling or causing other visible change in the surface appearance when viewed under a magnification of up to 100.
  • the organic solvent does not dissolve or swell the structure of the polymeric material but instead merely penetrates the surface layer while causing substantially no visible change in the surface appearance.
  • solvents such as tetrahydrofuran, dioxan, aliphatic ketones and acetates would be useful for swelling the surface, but in fact it is desirable to avoid such solvents in the method of the invention.
  • the organic solvent being used has too powerful an effect, and thus either swells the surface or penetrates deeper than is desired, it is possible to moderate this by inclusion in the reactant of an inert cosolvent or by emulsifying it in water or other inert liquid, or by both emulsification and the use of a cosolvent. This is described in more detail below.
  • the desired depth of the surface layer will depend partly upon the nature of the adherent coating. Generally it is not more than 5 microns and for many purposes is less than 1 micron. However it should normally be at least 0.05 microns in thickness, preferably 0.1 to 0.5 microns.
  • the first reactant preferably penetrates the surface to the depth desired for the surface layer.
  • the organic solvent in the first reactant will be chosen having regard to the nature of the polymeric material and having regard to the second reactant that is to be used.
  • the second reactant is an oxidising agent it is desirable to use as the first reactant an organic liquid that will react with such oxidising agent with a redox reaction that forms gaseous products.
  • Suitable reactants include heterocyclic compounds and in particular derivatives of pyridine or pyrrole.
  • Preferred reactants are keto derivatives of pyrrole, including keto derivatives of partially or fully saturated pyrroles, that is to say pyrrolidones and pyrrolinones.
  • Preferred reactants comprise N - methyl - 3 - pyrrolin - 2 - one and N - methyl - 2 - pyrrolidone. Very satisfactory results can be obtained using Russian White turpentine.
  • Some solvents used as part or all of the first reactant may have a swelling or dissolving effect on the polymeric material that is too powerful or may attack apparatus in which the process is to be conducted or may have an unpleasant odour.
  • the solvent diluted with an organic diluent or emulsified in water or both Any. inert compatible organic diluent can be used but alkyl ethers or diethylene glycol or ethylene glycol are preferred, especially the mono-n-butyl ether of ethylene glycol.
  • the proportion of the chosen heterocyclic liquid to any other organic liquid is generally from 0.5:1 to 5:1, most usually about 1:1 to 3:1 (parts by volume).
  • the organic liquid or liquids are used in the form of an emulsion in water.
  • concentration of organic liquid or liquids emulsified in water may be, for instance, from 40 to 70% and the emulsion may be stabilised by an appropriate emulsifying agent, such as ethoxylated castor oil.
  • excess of the first reactant is generally then removed, for instance by rinsing, and the second reactant may then be applied.
  • the second reactant generally comprises a chemical etchant for the polymeric material and thus is capable, when used under appropriate conditions (e.g. temperature and duration), of etching and degrading the polymeric material even in the absence of first reactant.
  • a chemical etchant for the polymeric material Preferably it is applied under conditions such that if it were used alone it would cause substantially no visible change in the surface appearance when viewed under a magnification of up to 100.
  • the etchant reacts preferentially with that reactant, and possibly also with the polymeric material in localised positions containing first reactant, to form pits in the surface layer while leaving the polymeric material between the pits substantially unreacted and undegraded.
  • the etchant is preferably one that reacts relatively violently with the first reactant when contacted in bulk. It may be an oxidising agent that will react with the first reactant with a redox reaction that forms gaseous products.
  • the oxidising agent or other etchant is usually an oxidising acid or mixture of acids and may be based on, for instance, nitric acid, sulphuric acid, phosphoric acid or chromic acid.
  • it comprises chromic acid both because of the desirable reactions that occur between chromic acid and the preferred first reactants and because of the strong penetrating properties of chromic acid.
  • the chromic acid is preferably introduced as an aqueous solution of from 200 to 600 g/I generally 350 to 500 g/l.
  • the second reactant is normally an aqueous solution. It may include surfactant.
  • the penetration of the surface layer with the first reactant is achieved by applying the first reactant by immersion, spray, brush or any other convenient technique for an appropriate duration and temperature.
  • the temperature is generally from ambient to 80°C.
  • excess first reactant is applied to the surface and is left in contact with the surface for from 0.5 to 10 minutes and excess solvent is then removed and the surface rinsed with hot water.
  • contact may be achieved by submerging the surface for a shorter period, e.g. up to 1 minute, in the first reactant. After removal of the excess solvent the surface may feel substantially dry to the touch.
  • Penetration of the second reactant into the surface layer followed by reaction of the reactants may be achieved by application of the second reactant by any convenient application technique, such as those discussed above, and maintaining the reactant in contact with the surface for from 2 to 20 minutes at from 40 to 80°C although shorter times are satisfactory if contact is by prolonged submersion, e.g. for up to 2 minutes.
  • the surface may then be rinsed with water and dried.
  • a cylindrical substrate is coated with an epoxy resin composition containing about 5% to 6% carbon and 1% molybdenum sulphide but free of substantially all other fillers by a powder coating technique followed by fusion of the surface. It is then diamond turned until it is smooth (even when viewed under 100 magnification) and then laser engraved to form the desired gravure cells.
  • a mixture is formed of one part by volume n-butyl ether of ethylene glycol (n-butyl Cellosolve, Cellosolve being a trade mark) and 2 parts by volume N - methyl - 3 - pyrrolin-2-one and this mixture is emulsified in water to form a 60% emulsion of the solvent mixture in water. 10% by weight of ethoxylated castor oil is included in the water as an emulsifying agent.
  • the surface is then water rinsed and then has applied to it aqueous chromic acid having a concentration of 400 to 480 gll and containing 5% to 10% by volume surfactant, for 5 to 10 minutes at 55 to 70°C.
  • the surface is then given a hot water rinse at about 65°C.
  • the surface is highly pitted (as viewed under a magnification of 100), with the pits extending less than 0.5 microns deep.
  • the surface is then contacted for from 5 to 10 minutes at 40 to 60°C with a solution of stannous chloride and 30% hydrochloric acid, in order to neutralise the surface. It is then rinsed and charged transfer is effected by immersing the surface for 2 minutes at 30°C in a 3% by volume aqueous solution of a cationic surfactant.
  • the surface is then rinsed in water again and is conditioned by contact with a 10% by volume solution of colloidal palladium in hydrochloric acid at 25 to 30°C for from 3 to 5 minutes followed by - rinsing and reduction of the colloidal palladium by treatment with a 10% by volume solution of hydrochloric acid containing a small amount of stannous chloride for 3 minutes at 40 to 50°C.
  • the surface is then again rinsed with water and is then subjected to electroless nickel deposition using an autocatalytic proprietory solution that deposits on the cylinder at 80 to 90°C at a rate of approximately 12 to 14 microns per hour.
  • Example 1 The process of Example 1 is repeated except that the N - methyl - 3 - pyrrolin - 2 - one is replaced by an equal volume of N - methyl - 2 - pyrrolidone. Similar results are achieved.
  • Example 1 The process of Example 1 is repeated except that the N - methyl - 3 - pyrrolin - 2 - one is replaced with an equal volume of Russian White turpentine.
  • a flat substrate formed of the same epoxy composition as in example 1 is immersed in the same solvent composition for 1 minute at 42°C, while another piece is immersed in the chromic acid solution at 68°C for 30 seconds. Both pieces are washed and dried and examined under 100 magnification. Neither treatment results in any noticeable change in the surface appearance.
  • the piece that has been solvent treated is then immersed in the same chromic acid solution at 68°C for 30 seconds and then rinsed. When viewed under 100 magnification the surface appears highly pitted. The pits extend to a depth of less than 1 micron. The pitted surface can then be neutralised and plated as described in Example 1.

Claims (15)

1. Procédé pour fabriquer un élément d'impression en taille-douce dans lequel une couche superficielle qui est formée d'une matière polymère et qui est gravée avec des cellules en taille-douce et qui a essentiellement des caractéristiques de non-impression entre les cellules est préparée pour recevoir un revêtement adhésif par application d'un réactif, caractérisé en ce que le procédé consiste à faire pénétrer la couche superficielle seulement par un premier réactif et ensuite par un second réactif et à faire ou laisser réagir le second réactif avec le premier réactif à l'intérieur de la couche superficielle pour former des creux qui s'étendent depuis la surface dans la couche superficielle pratiquement sans dégradation chimique de la matière polymère entre les creux.
2. Procédé selon la revendication 1, caractérisé en ce que l'on applique ensuite à la surface creusée un revêtement métallique adhérent par métallisation non-électrolytique.
3. Procédé selon la revendication 1 ou 2, caractérisé en ce que le premier réactif comprend un solvant organique et pénètre sans la couche superficielle pratiquement sans gonflement ou dans provoquer d'autres changements visibles de l'aspect de la surface lorsqu'on l'examine à un groississement allant jusqu'à 100.
4. Procédé selon la revendication 3, caractérisé en ce que le premier réactif comprend un dérivé céto d'un pyrrole qui peut être partiellement ou complètement saturé.
5. Procédé selon la revendication 4, caractérisé en ce que le premier réactif comprend de la N - méthyl - 2 - pyrrolidone ou de la N - méthyl - 3 - pyrroline - 2 - one.
6. Procédé selon la revendication 4, caractérisé en ce que le premier réactif comprend de la térébenthine de Blanc de Russie.
7. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que le second réactif comprend un agent chimique d'attaque qui est appliqué à une température et pendant une durée telles que, si on l'utilise sans le premier réactif, il ne provoque pratiquement pas de changements visibles de l'aspect de la surface lorsqu'on l'examine à un grossissement allant jusqu'à 100 fois.
8. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que le second réactif comprend un agent oxydant qui réagit avec le premier solvant selon une réaction d'oxydoréduction pour former des produits gazeux.
9. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que le second réactif comprend de l'acide chromique.
10. Procédé selon l'une quelconque des revendications précédentes; caractérisé en ce que la couche superficielle a une épaisseur de moins de 5 um.
11. Procédé selon la revendication 10, caractérisé en ce que la couche superficielle a une épaisseur de 0,05 à 0,5 pm.
12. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que la pénétration du premier réactif est contrôlée en le fournissant sous forme d'une solution dans un cosolvant inerte ou dans une émulsion dans l'eau, ou les deux.
13. Procédé selon la revendication 12, caractérisé en ce que le premier réactif est fourni sous forme d'une émulsion aqueuse à 40-70% en volume d'un mélange de 0,5 à 5 parties en volume d'un dérivé céto d'un pyrrole, qui peut être partiellement ou totalement saturé, ou de térébenthine de Blanc de Russie avec une partie en volume d'un cosolvant inerte.
14. Procédé selon la revendication 12 ou 13, caractérisé en ce que le cosolvant est un éther d'alkyle d'éthylèneglycol ou de diéthylèneglycol.
15. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que la matière polymère est une résine époxy contenant moins de 20% de charge.
EP19810305262 1980-11-20 1981-11-05 Revêtement de substrats polymériques Expired EP0052968B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8037294 1980-11-20
GB8037294 1980-11-20

Publications (3)

Publication Number Publication Date
EP0052968A2 EP0052968A2 (fr) 1982-06-02
EP0052968A3 EP0052968A3 (en) 1982-12-22
EP0052968B1 true EP0052968B1 (fr) 1986-02-26

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Family Applications (1)

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EP19810305262 Expired EP0052968B1 (fr) 1980-11-20 1981-11-05 Revêtement de substrats polymériques

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EP (1) EP0052968B1 (fr)
JP (1) JPS57115429A (fr)
DE (1) DE3173905D1 (fr)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4848348A (en) * 1983-11-14 1989-07-18 Minnesota Mining And Manufacturing Company Coated films
US5049230A (en) * 1988-11-07 1991-09-17 Jp Laboratories, Inc. Single step pre-swelling and etching of plastics for plating
US5015329A (en) * 1988-11-07 1991-05-14 Jp Laboratories, Inc. Pre-swelling and etching of plastics for plating
US4941940A (en) * 1988-11-07 1990-07-17 Jp Laboratories, Inc. Pre-swelling and etching of plastics for plating
DE4228596A1 (de) * 1992-08-27 1994-03-03 Metallgesellschaft Ag Tiefdruckzylinder
DK1182966T3 (da) 1999-05-25 2004-04-13 Medicotest As Elektrode til påsætning på huden
DK1301123T3 (da) 2000-07-19 2005-01-24 Medicotest As Hudelektrode med et bypass-element
JP5266944B2 (ja) 2007-08-08 2013-08-21 住友化学株式会社 α−不飽和アミン化合物の分離精製方法
EP2514594A1 (fr) * 2011-04-18 2012-10-24 KBA-NotaSys SA Plaque d'impression en creux, son procédé de fabrication et utilisation correspondante
WO2024070387A1 (fr) * 2022-09-29 2024-04-04 東レ株式会社 Composition de résine, film durci et dispositif à semi-conducteur

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3518067A (en) * 1965-08-20 1970-06-30 Union Carbide Corp Method of plating polyarylene polyethers,polycarbonate or polyhydroxyethers and the resulting articles
GB1175348A (en) * 1967-07-13 1969-12-23 Okuno Chemical Industry Compan Process for Chemically Plating Polyolefins.
BE793615A (fr) * 1972-01-03 1973-05-02 Shipley Co Procede de traitement d'un substrat de matiere plastique pour la formation d'un depot chimique de metal
GB1381243A (en) * 1972-02-18 1975-01-22 Kollmorgen Corp Method for metallizing substrates
HU166605B (fr) * 1973-03-29 1975-04-28
GB1524717A (en) * 1975-06-17 1978-09-13 Crosfield Electronics Ltd Coating non-conductive surfaces
JPS5418875A (en) * 1977-07-12 1979-02-13 Nippon Denki Kagaku Co Ltd Pretreatment for nonnelectrolytic copper plating on epoxyresin substrate

Also Published As

Publication number Publication date
DE3173905D1 (en) 1986-04-03
EP0052968A2 (fr) 1982-06-02
JPS57115429A (en) 1982-07-17
EP0052968A3 (en) 1982-12-22

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