Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F3/00—Colour separation; Correction of tonal value
  • G03F3/10—Checking the colour or tonal value of separation negatives or positives

Definitions

• This invention relates to actinic radiation- sensitive elements for colored image reproduction and more particularly to elements wherein positive images are formed for the purposes of proofing the color separations of original, multi-colored, renditions of graphic art.
• U.S Patent 3,136,637 discloses the use of a multiple layered negative acting proofing system.
• each of the colored sheets which have been exposed with the appropriate separation negative are developed and then superimposed one on top of the other in exact register.
• These transparent sheets containing the colored images in exact detail can then be examined individually or in total to recognize any deficiencies compared to the original piece of graphic art prior to the manufacture of the printing plates.
• U.S. Patent 3,671,236 the same objective as above is attained by superimposing on a single substrate the several colored layers so that the composite structure more closely resembles the final printed specimen.
• This process is again a negative acting system wherein a litographic negative is the means whereby the information is transferred photomechanically to the colored proofing sheets.
• Still another proofing system is disclosed in U.S. Patent 2,993,788 wherein a lithographic negative is used to expose a positive acting diazo oxide-sensitized substrate.
• a lithographic negative is used to expose a positive acting diazo oxide-sensitized substrate.
• a dye of a predetermined color using the non-exposed portions of the diazo oxide as a photomask
• a single sheet, negative acting proofing composition is attained.
• a common problem is always cited; namely, preserving the background or non-imaged portions of the proof from unwanted staining or discoloration (i.e., toning), which degrades the overall value of the composite proof.
• the present invention relates to a presensitized sheet material and an associated proofing method which substantially eliminates such discoloration in the proofing sheet.
• the presensitized color proofing sheet of the present invention is comprised of a carrier sheet having a smooth release surface.
• Clingingly adhered to the release surface of the carrier sheet is a color coating which is a mixture of a diazo oxide and a pigmented base soluble resin compound.
• clingingly adhered it is meant that the release value is between 2-60 grams per 2 lineal inches, with between 4 to 20 being preferred, as tested by the procedures described in TAPPI (Technical Association for the Pulp and Paper Industry), vol. 43, No. 8, pp. 164A and 165A (August 1960).
• Bonded to the top of this color coating is a discrete binder layer of a mixture of a base-soluble resin and a diazo oxide. Both the binder layer and the color coating are solubilizable in a solvent developing medium upon exposure to actinic radiation but not solubilizable in the developing medium prior to exposure to actinic radiation. Firmly attached to the binder is a clear barrier layer which is insolubilizable in the development medium.
• the barrier layer of a first presensitized sheet of the aforementioned construction is bonded to a substrate and the carrier sheet removed.
• the substrate with the presensitized proofing sheet bonded thereto is then exposed to actinic radiation through a color separation positive corresponding to the pigment of the color coating.
• the exposed diazo oxide and resin mixture in the binder layer and the color coating is rendered soluble to a solvent developing medium to create a latent image.
• the latent image may then be developed with a solvent developing medium whereby the exposed diazo oxide and resin mixture in the binder layer and associated color coating is removed leaving the unexposed diazo oxide and resin.
• the aforementioned process is repeated in sequence and in register so that the composite proof contains colored layers representing the magenta, cyan, yellow and black contributions of the original subject matter.
• the solvent-resistant barrier layer composed as part of the subsequent presensitized sheet to be imaged, provides protection for the already imaged and developed presensitized sheet laid down previously on the substrate.
• Figure 1 shows a broken away edge view of a photosensitive color proofing sheet.
• Figure 2 likewise, a broken away edge view, shows the structure having been laminated to a substrate after removing the temporary carrier sheet and having been exposed to actinic radiation through a positive acting lithographic film.
• Figure 3 shows the non-exposed portions of the colored proofing film remaining intact whereas, the actinically exposed portions have been removed by a solvent development medium.
• Figure 4 is intended to show a second colored layer of a presensitized proofing sheet in place over the previously developed color layer just prior to bonding and exposure of the second color proofing sheet.
• a carrier sheet 20 is provided with a release surface 18 which may either be a smooth surface of the carrier itself or a surface coating thereon.
• the function of release surface 18 is to serve as a parting layer between the carrier sheet 20 and the color layer 16.
• Carrier sheet 20 may be made of numerous materials which are known in the art.
• the preferred material for use in the present invention is a 0.002 inch ⁇ 2 mil) thick polyester film which has a release surface 18 consisting of a coating of a methyl ether of cellulose, e.g, Methocel A-15 sold by Dow Chemical of Midland, Mich.
• Color layer 16 is composed of a light-sensitive, positive-acting diazo oxide dispersed in a solvent soluble resinous binder system in which a pigment representing one of the process colors used in the printing of four color lithography has been dispersed.
• Overlying color layer 16 is a continuous binder layer 14 of resin and a diazo oxide mixture or reaction product whose function is to provide for clean release of color layer 16.
• a continuous binder layer 14 of resin and a diazo oxide mixture or reaction product whose function is to provide for clean release of color layer 16.
• toning is eliminated because the binder layer is free of color pigment.
• Binder layer 14, in its non-exposed state is a clear film containing little or no optical haze and so does not detract from the color remaining in the imaged area.
• the diazo oxide used in color layer 16 and binder layer 14 be selected from the group of orthoquinone diazides.
• the preferred orthoquinone diazide for use in the present invention is the napthoquinone- (l,2)-diazido-(2)-5-sulfo-acid ester of 4-tertiary butylphenol.
• Binder layer 14 is coated from a solvent system that will minimize the penetration of the resinous binder layer 14 into the color layer 16. That is, the pigment in the color layer must not be soluble in the solvent and to coat the binder layer.
• the ultimate selection of the solvent system is greatly influenced by the drying conditions which will be utilized. It has been found that solvent such as the lower molecular weight alcohols, e.g., methanol, ethanol, n-propyl and isopropyl alcohol, are satisfactory in most cases.
• an aqueous alkaline developer is required to bring forth the latent image.
• the resins used in dried layers 14 and 16 should be only slightly penetrable by the aqueous alkaline developer. Examples of such resins are the phenol-formaldehyde novalak resins and other similar resins with sufficient carboxy or hydroxy functionality to allow for penetration by an aqueous base.
• binder layer 14 may be the reaction product of an alkali-solution of a phenol formaldehyde resin ⁇ e.g., Reinox available from Monsanto of St. Louis, Mo.) and 2-diazo-l-naphthol-5-sulfonyl chloride.
• the reaction product has been found to give a greater latitude in the choice of developers because of its resistance to attack. Further the reaction product has been found to have greater resistance to solvents used for coating the barrier layer 12 which enables binder layer 14 to retain a discrete character.
• Adhered to binder layer 14 is a solvent barrier layer 12, whose function is to bond the exposed and developed structure to a permanent base, as well as to protect the image areas of the first laid down color from subsequent development by solvent when the second, third and fourth colors are positioned in place and in register. Because the positive acting diazo oxide containing image portions of a particular color coating 16 and binder layer 14 are still light sensitive after subtracting away the exposed portions, barrier layer 12 acts to protect previously formed image (s) from deterioriation due to developer solvent penetration.
• Barrier layer 12 is comprised of a thermally activated adhesive which is coated on the top surface of the binder layer 14.
• a pressure sensitive adhesive may be used by bonding it directly to an already coated resin having the solubility characteristics of the thermally activated adhesive.
• the adhesive is preferably a thermally activated type, i.e. methyl methacrylate, n-butyl methacrylate, n-butyl/isobutyl methacrylate, polyvinyl acetals and polystyrenes. Latices may also be used but due to the presence of the emulsifiers there may be a tendency to attack color layer, so special care in the selection must be taken.
• the aforementioned resins may be coated from solutions wherein the solvents are straight chain hydrocarbons (C 2 to C 6 ) as well as saturated and aromatic cyclic hydrocarbons, e.g. cyclohexane, toluene, etc.
• the adhesive may be moisture sensitive or pressure sensitive e.g. U.S. Patent 3,671,236.
• the adhesive surface of the barrier layer 12 may be protected from contamination by dirt or grease, by a protective release liner 10 made of materials such as silicone coated paper and the like.
• the release liner 10 is removed and the remaining composition is inverted from the position that is shown in Figure 1 so that barrier layer 12 is placed in contact with the substrate 30 and the two bonded together ( Figure 2).
• a suitable paper for substrate 30 is a heat stable, waterproof white paper designated as P-350 which is available from Schoeller Technical Paper Sales, Inc. of Pulaski, New York.
• the lamination process may be accomplished by inserting the substrate 30 and the inverted proofing sheet comprising layers represented by 12, 14, 16, 18 and 20 between a pair of nip rolls heated to 250°F. and passing the composite between these rolls at a linear speed of about 30 inches/minute.
• Figure 2 is intended to illustrate this inversion process and the subsequent lamination of the adhesive layer 12 to the paper substrate 30 with carrier sheet 20 and the associated release surface 18 removed.
• Figure 2 further represents the mounted presensitive sheet of the present invention which has been exposed through a positive transparency. After such an exposure, binder and color layers 14b and 16b become solubilizable due the action of the actinic radiation on the diazo oxides whereas the non-exposed portions represented by 14a and 16a remain non-solubilized.
• the preferred developing solution is comprised of 1.5% sodium metasilicate and 0.10% wetting agent such as a sodium alkylnaphthalene sulfonate (e.g. Nekal NF sold by GAF Corporation of New York, New York).
• a sodium alkylnaphthalene sulfonate e.g. Nekal NF sold by GAF Corporation of New York, New York.
• the remaining imaged structure after drying is then ready to receive a second presensitized proofing sheet of a different process color than was previously laminated to substrate 30.
• This is best represented by Figure 4.
• the adhesive of the barrier layer 12 is shown in contact with imaged color layer 16a just prior to thermal lamination. It must be recognized that layers 14a and 16a represent only a few thousands of an inch in total thickness and that when laver 12 is laminated to the imaged section below, the result is essentially a planar surface.
• a presensitized proofing sheets made in accordance with the present invention prior to storage may be sealed in a polyethylene package so as to protect the release layer from moisture attack.
• the sheet may then be stored in sensitized condition and then used weeks or months later as successfully as immediately following manufacture.
• EXAMPLE 1 A carrier sheet of a 2-mil film of biaxially oriented polyethylene terephthalate polyester was first coated with a methyl ether of cellulose solution constituted as follows:
• Methyl ether of cellulose available as 1.5
• a dry coating weight of 50 to 70 mg/ft 2 provided a satisfactory release layer.
• a release value of 4 grams per 2 lineal inch appeared to be an acceptable lower limit as measured by TAPPI Standards and a workable maximum value of 50 grams per 2 lineal inches.
• This release layer was then dried and a coating solution for the color layer was prepared by first preparing a urethane reaction product, as follows:
• Diisocyanate (D.D.I. 1410 1.4 7.38 available from General Mills of Minneapolis, Minn.) Triethylene diamine (T.E.D.A.) 0.1 0.37 Methyl ethyl ketone 72.0
• the urethane reacted product After mixing for approximately 18 to 20 hours at room temperature, the urethane reacted product produced a reading of 10-11 cps. when measured on a Brookfield Viscometer with a #1 spindle and a speed of 60. This urethane reaction product solution was then used to prepare the millbase containing the colored pigments, chosen so that they bear a close correlation to the pigment colors used in printing inks.
• the procedure followed in combining the various components of the millbase includes first dissolving the polyvinyl butyral in the reacted urethane solution. The Monastral blue pigment was then added to the mixture which was then sand milled as needed to give a very fine grind. To this milled base was mixed an amount of diazo oxide (naphtoquinone-(l,2)-diazido-(2)-5-sulfo-acid ester of 4-tertiarybutylphenol) equal to 25% of the amount of urethane dry solids content.
• diazo oxide naphtoquinone-(l,2)-diazido-(2)-5-sulfo-acid ester of 4-tertiarybutylphenol
• the color layer was then coated on the previously prepared carrier sheet using a #6 meyer bar diluting with MEK as required to obtain a 1.25 ROD (Reflection Optical density) reading using a Wratten ® R-25 filter (MacBeth TR-524 Dens).
• a binder layer solution was prepared having as its composition:
• the binder layer was then coated on the previously applied color layer by means of a #22 meyer bar to a coating weight of between 20 to 30 mg/ft 2 .
• a barrier layer was prepared comprising:
• Example 1 A structure in Example 1 was prepared. An adhesive layer of a colorless pressure-sensitive adhesive
• EXAMPLE 3 A structure having a carrier sheet and a color layer was made as outlined in Example 1. A binder layer was prepared by charging the following into a quart jar fitted with a stirrer (Note - each compound was dissolved before the addition of the subsequent compound):
• NaHCO 3 available from Mallinchrodt 16.1 grams Chemical Co. of St. Louis, Mo.
• the resulting precipitate was filtered and washed until the wash water was free of acid as measured by pH.
• the solid collected was then dried at room temperature with moderate air movement to remove the water as determined by the attainment of constant weight. The percent yield averaged 90%.
• Example 1 To prepare the binder coating solution 1.5 grams of the above dried solid was dissolved in 98.5 grams of isopropanol. This was then applied to the color coating as described in Example 1. A barrier layer was prepared and applied to the surface of this binder in similar manner as that of Example 1.
• the lower limit on a mole ratio basis has been found to be approximately 5.5 moles of the phenolic resin per mole of pendent diazo oxide.
• the upper limit has been found to be approximately 2 moles of pendent diazo oxide per mole of the phenolic resin.

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• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
• Heat Sensitive Colour Forming Recording (AREA)
• Photosensitive Polymer And Photoresist Processing (AREA)

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• 1979
  • 1979-09-05 US US06/072,634 patent/US4260673A/en not_active Expired - Lifetime
• 1980
  • 1980-08-01 CA CA000357542A patent/CA1143989A/en not_active Expired
  • 1980-08-04 DE DE8080901776T patent/DE3071145D1/de not_active Expired
  • 1980-08-04 BR BR8008810A patent/BR8008810A/pt not_active IP Right Cessation
  • 1980-08-04 JP JP55502098A patent/JPH0235290B2/ja not_active Expired - Lifetime
  • 1980-08-04 WO PCT/US1980/001004 patent/WO1981000772A1/en not_active Ceased
  • 1980-09-04 BE BE0/201987A patent/BE885085A/fr not_active IP Right Cessation
  • 1980-09-04 IT IT24458/80A patent/IT1132651B/it active
• 1981
  • 1981-03-23 EP EP80901776A patent/EP0035028B1/en not_active Expired

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