POSITIVE, LAMINABLE PROOFING CONSTRUCTION

Abstract: Positive-acting, laminable imaging constructions often suffer from high levels of optical density in background areas. The optical density is provided by migratory colorant or photo-­ sensitive diazo oxide. The use of a base soluble organic binder with a substantially polar solvent which contains the colorant and diazo oxide in combination with a thermally softenable polymeric adhesive layer having a substantially non-polar solvent system prevents migration of colorant and diazo oxide between layers and reduces the background optical density.

Description: POSITIVE, LAMINABLE PROOFING CONSTRUCTION Background of the Invention Field of the Invention The present invention relates to positive-acting printing proofs and, in particular, to laminable positive proofs for providing color separations of original, multicolored renditions of graphic art. Description of the Prior Art In the photomechanical process of reproducing the tone values and color shades represented by a piece of original graphic art, it is necessary to prepare a series of color separations by photographic means so that the particular colors to be printed are first recorded on a set of separation negatives or positives by means of appropriate filtering and masking techniques. By following known procedures, four photographic black and white separation negatives or positives are made representing the three process colors, magenta, cyan and yellow, as well as the fourth representing the black contribution. These separations are then used to make four printing plates. These plates are then mounted on an offset printing press to recreate a rendition of the original piece of art. In some instances, the printing press is not faithful in its reproduction of the copy carried by the printing plates because of inherent limitations in the printing process. In other instances, the buyer of the printed copy may desire changes in tonal values so that the printed matter as represented by the output of the press is more satisfying to his customers. For these reasons and others, a method of previewing the results before actually printing the subject matter has been devised whereby the changes and adjustments may be made to the separation transparencies prior to the manufacture of the printing plates. One method of previewing the color separation of an original colored piece of art work is disclosed in U.S. Patent No. 3,136,637. This patent discloses the use of a multiple layered negative-acting proofing system. In this 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 discover any deficiencies as the individual or combined sheets are compared to the original piece of graphic art prior to the manufacture of the printing plates. In U.S. Patent No. 3,671,236, the same objective 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 is a negative-acting system, wherein a lithographic negative transfers the information photomechanically to the colored proofing sheets. Still another proofing system is disclosed in U.S. Patent No. 2,993,788, wherein a lithographic negative is used to expose a positive-acting diazo oxide sensitized substrate. By first exposing and developing the sensitized substrate and then applying a dye of predetermined color (using the non-exposed portions of the diazo oxide as a photomask), a single sheet, negative-acting proofing composition is obtained. In the performance of the prior art methods of generating color proofs from either positive or negative separations, a common problem is generally cited. The background or non-imaged portions of the proof are difficult to preserve from unwanted staining or discoloration (i.e., toning), which degrades the overall value of the composite proof. U.S. Patent No. 4,260,673 overcomes the problem of unwanted staining by placing a barrier layer between the color containing layer and other layers which are part of the final proof image. The barrier is particularly effective when placed between the colorant containing layer and the thermal adhesive layer. The addition of another layer increases the cost of manufacturing the sheet and introduces additional variables (such as additional chemicals and transmissivity) into the performance of the sheet. Summary of the Invention The photosensitive, positive-acting color proofing sheet of the present invention comprises at least two layers, a thermal adhesive layer and a positive-acting, color containing, photosensitive layer. The polymer and solvent systems of these two respective layers are selected so that the colorant or active components of the photosensitive layer are not highly soluble in the polymer and solvent material of the thermal adhesive layer and therefore will not migrate into the thermal adhesive layer. Description of the Invention The color proofing sheet of the present invention comprises at least two layers. One layer is a thermal adhesive layer and the other layer is a colorant-containing, positive-acting photosensitive layer. Additional layers such as a strippable carrier layer with or without a release coating on one face thereof which is in contact with the photosensitive layer is a preferred construction. A strippable cover layer may also be advantageously used over the thermal adhesive layer. A release layer may also be bonded to the photosensensitive color layer which remains adhered to the color when the sheet is stripped from a base film or carrier layer. 1'he photosensiL-ive layer comprises a base soluble organic polymeric resin binder having an o-quinone diazide or other positive-acting diazo oxide mixed with, dissolved in, or pendant to the binder. The layer also contains colorant such as a pigment or dye. The diazo oxide must be soluble or otherwise present in amounts of at least 15% by weight in the organic polymeric resin binder. Preferred polymers for this layer are phenolic resins including both resols and novalaks. Base soluble acrylic resins are also useful. The solvent system used during the coating of the photosensitive layer (and the other layers) can have a dramatic effect in the practice of the present invention. Polar solvents, or at least substantially polar solvent mixtures should be used in the coating of this layer. Examples nit useful polar solvents include ketones (methyl ethyl ketone, methyl isobutyl ketone, etc.), alcohols or ethers (glycol monomethyl ether, glycol monoethyl ether, ethoxy ethyl acetate), halogenated hydrocarbons (trichloroethane, etc.), esters (ethyl or butyl acetate), and mixtures of those polar solvents, together or with small amounts (less than 20% by volume, preferably less than 10% by volume) of non-polar solvents such as intermediate length hydrocarbons (pentane, hexane, heptane, octane, etc.). These mixtures of small amounts of non-polar solvents and polar solvents constitute the substantially polar solvent mixtures referred to above. The base-soluble organic polymeric binder (i.e. soluble or readily dispersible in aqueous alkaline solution of pH 13) for the photosensitive layer, as indicated above, is preferably a phenolic resin. Other polymeric materials (such as butvar resin to disperse and hold the colorant) may be diss(?# #e# or fli xed with that primary resin binder constituent. Epoxy resin may also be mixed or dissolved with the binder to adjust physical properties. Furthermore, crosslinked epoxy or polyurethane resin may be added as may polyisocyanates (or other epoxy resin crosslinking agents) and monoisocyanates to react with the phenolic rin or other polymer constituents. The thermal adhesive layer comprises an organic polymeric, thermoplastic binder which is not developed (disso#vc¯ct. )r softened ;() as to be readily relnove by hand-rubbing with a developer pad) in an aqueous, alkaline solution of pil 13. Any thermoplastic resin softenable at a temperature of less than 2000C, preferably at less than 1750C and most preferably at a temperature less than 1600C (with a preferred range between 1000C and 1600C) is useful as the binder component of this layer if it is not soluble in an aqueous alkaline developer. Preferred polymers are not tacky at 200C and include, for example, polyenes (styrene, butadiene, acrylonitrile polymers, copolymers and terpolymers), acrylics (e.g., methylmethacrylate, n-butyl acrylate, col)()lymers lhereof, etc.), etc. These polymers are coated out in a solvent which is not completely miscible (and preferably immiscible) in the coating of the photosensitive layer and which is preferably a non-polar solvent or at least substantially non-polar solvent. Solvents such as nonpolar aromatic hydrocarbons (toluene, benzene and the like), and aliphatic hydrocarbons (e.g., intermediate length hydrocarbons such as pentane, hexane, heptane, octane, etc.) are particularly preferred. To the extent that any non-polar solvents are used in coating the photoscnsiiive layer with substantially polar solvent mixtures, the non-polar solvents used in the coating of the thermal adhesive layer may be different from the non-polar solvent in the photosensitive layer. Substantially non-polar solvents, as the term is used in the present invention allows for less than 20% by volume of a compatible polar solvent and preferably less than 10%. In the most preferred practice of the present invention, polar solvents are used in the coating of the photosensitive layer, and non-polar solvents are used in the coating of the thermal adhesive layer. The presence of less than 5% of the total solvent of the opposite type of solvent in the ompoiions used to coat each layer is usually quite sufficient to prevent migration of colorant or diazo oxide between layers. The diazo oxide is itself colored (usually yellow) and should remain in constant concentration in the photosensitive layer, so that it also should be prevented from migrating into the thermal adhesive layer. Any dye or pigment may be used in the photosensitive layer as the colorant. Generally such layers comprise either cyan, magenta, yellow or black colorants. Both organic and inorganic colorants may be used. It is preferred that such colorants not be sensitive (oxidizable, colorizable, or degradable) to aqueous alkaline solutions since they may well be in contact with developer solutions. The diazo oxide selected should be chosen at least in par- on the oasis of its relative solubility properties between the photosensitive layer and the thermal adhesive layer. Because the diazo oxides tend to have a yellow color to them, their migration between layers would provide some yellow stain in the background. As diazo oxides are sonewhat polar, they would tend to generally have a natural affinity for remaining in the photosensitive layer (with its generally polar solvent) than for migrating into the thermal adhesive layer (with its generally non-polar solvent). Selection of diazo oxides with greater degrees of polarity or particularly great affinity for the particular resin binder used in the photosensitive layer or particularly high insolubility in the polymeric binder used in the thermal adhesive layer should be used to enhance this resistance to migration between layers. Diazo oxides with sulfony# iinkinq groups to aromatic groups (such as 2,4-(dioxy-5-sulfonyl- [ naphthoquinone-2-diazido ] )- benzophenc#ne) are par-ictilarly useful in this regard. The diazo oxide is present in an amount from 6-50 percent by dry weight of the photosensitive layer, preferably as 10-33 percent by dLy weight of the layer. The prepared diazo oxides according to the present invention co1fl#)rise monofunctional diazo oxides having a molecular weight greater than or equal to 400 and polyfunctional (at least difunctional) diazo oxides having molecular weights greater than or equal to 350. It is more preferred that the diazo oxide groups contain polar groups. At least one strongly polar group (as strong or stronger than carboxyl) such as sulfonamide, amide, urea, and carboxyl, or at least two moderately strong polar groups (as strong or stronger than ethers) such as esters, ketones, hydroxyls, amines, throethers and ethers are preferred. Even where the diazo oxide is bound into the polymer chain of an ingredient of the color layer, imcompatible solvents are used to prevent interpenetration of other layers by the diazo oxide. Each of the four colors may be added into separate layers of this general construction. These and other aspects of the present invention will he shown in the following examples. Example 1 The example described below outlines the procedure for production and imaging of a magenta image. A qualitatively similar procedure may be followed for each of the other three colors. Onto a 2-mil polyethylene terephthalate carrier film was coated a release layer having a dry coating weight of 70-80 mg/ft2. The Hollowing solution was extrusion-bar coated as the release layer on the carrier film, then oven dried at 190 F-200 F. Deionized water 72.9 lbs Gelvatol@ 20/30 polyvinyl alcohol 2758 g 25/30 polyvinyl alcohol 2758 g Gelvatol@ 2()/90 polyvinyl alcohol 919 g Triton@ X-100 surfactant 40 g Once this layer was dried, it was overcoated with the photosensitive color solution. This color solution was prepared in two stages: first, a millhase was made consisting of jhe following materials: modified Resinox ied1#flc)X [ a reaction product of Resinox RS 7280 (Monsanto) and ;t" I)y weight of DDI-1410 diiso cyanate (llenkel) ] as a 29.2% solids solution in MEK 1360 g (methyl ethyl ketone) Butvar B-76 dispersant (Monsanto) polyvinyl butyral resin 43 g Watchung Red Pigment 698-D 170 g Cabot Regal Black Pigment 300R 2 g After complete milling, more modified Resinox was added in the amount of 1360 g Using this millbase, the actual coating solution was made up within 24 hours ot coating: : Millbase (adjusted to 31.15% solids) 1335 g Benzophenone bis diazo oxide 84 g Additional MEK 1330 g This solution was double-roll coated onto a silicone treated release layer to a green-filter color density of 1.25, giving a dry thickness of approximately 100 mg/ft2 after oven-drying at 1900F-2050F. Finally, the adhesive solution was extrusion-bar coated directly on top of the color layer, and dried at 1500F-2O00F to a final thickness of about 500 mg/ft2. This solution was made up of 85 g of Pliolite S-5-A styrene-butadiene copolymer (Goodyear) and 920 g of toluene. A sample of this positive-acting color proofing sheet was heat-pressure laminated at 2750F roll setting to a white paper base (made by Schoeller Technical Paper Sales, Inc.). The green-filter densitometer reading for this coating indicated a magenta density of about 1.45. This laminate was exposed through a positive photomask to a high-density UV light source for 6-7 seconds (30 units), and then given the standard aqueous, alkaline development at pH 13. This afforded an image with excellent resolution and virtually no (densitometer readings less than 0.01) background color. Example 2 A solution was prepared in two stages. First, a cyan millbase was made consisting of the following material: Modified Resinox (as in Example 1) 24 ibis. Butvar B-76 (polyvinyl butyral) 430 g Monastral Issue BT-297-D pigment 1160 g Monastral Blue BT-284-D pigment 550 g After complete milling, more modified Resinox was added 24 libs. After this solution had been diluted to 31% solids by addition of methyl ethyl ketone, a coating solution was made up by mixing the following: Millbase, 31% solids 10 g Diazo-Resinox, a reaction product of Resinox (42g) and napthoquinone 2-diazido-5-sulfonyl chloride (36g) 0.95 g Methyl ethyl Ketone 13.5 g This coatlnj solution wa applied in the same manner on the release layer of Example 1, After coating this solution within 24 hours of preparation and oven-drying at 2000F, the adhesive layer was prepared and applied as in Example 1. After heat-pressure lamination to white paper base, a yellow-filter densitometer reading indicated a cyan reflectance density of 1.48. After a short exposure to UV light through a positive photomask and aqueous alkaline (pH 13) development, an image with good resolution and no background color was obtained. Example 3 Example 2 was repeated up to the second stage of color-codt solution preparation. The final color coating solution was epare by mixing the following: Cyan Millbase (Ex. 2), 31% solids 10 g Bis-diazo oxide amide, a reaction product 1 mol of 1,3-bis-aminomethyl cyclohexane and two moles of naptho quinone-2-diazido-5-sulfonyl chloride 0.60 g Additional methyl ethyl ketone 11 g This solution was coated onto the release layer described in Example 1 and oven-dried at 2000F. On top of this was coated the adhesive layer described in the earlier examples. After heat-pressure lamination to white paper base, a yellow-filter densitometer reading of 1.3 obtained. The laminate was exposed to UV light through a positive photomask for 3 seconds and subjected to aqueous alkaline development, affording an excellent cyan image with no background coloration. Example 4 On top of the release and color layers described in Example I was coated the following adhesive solution: Pliolite S-5-A 10 g Methyl ethyl ketone 5 g Toluene 95 g This coating was oven-dried at 200 oF for 2 minutes, then heat-pressure laminated to white paper base. After exposure and processing as in Example 1, a good magenta image with little or no (densitometer reading less than 0.02) back##rc#und coloration was obtained.

Claims: Claims: 1. A positive-acting, laminable imaging construction comprising: a) a first layer of a base-soluble organic polymeric binder layer having a diazo oxide compound or diazo oxide pendant group on the polymer binder present as at least 15 percent by weight of the binder and sufficient colorant to provide a transmission optical density of at least 1.0, and b) a thermal adhesive layer second layer comprising a thermally softenable polymeric adhesive layer, said first layer having at least a substantially polar solvent system with less than 20 percent by volume of all solvents of a non-polar solvent, and said second layer having at least a substantially non-polar solvent system with less than 20 percent by volume of all solvents of a polar solvent. 2. The construction of claim 1 wherein the solvent system of said first layer has less than 10 percent by volume of a non-polar solvent and said diazo oxide is selected from the group consisting of a monofunctional diazo oxide having a molecular weight equal to or greater than 400 and a polyfunctional diazo oxide having a molecular weight equal or greater than 350. 3. rrhe construction of claim 1 wherein the solvent system of said second layer has less than 10 percent by volume of a polar solvent. 4. The construction of claim 2 wherein the solvent system of said second layer has less than 10 percent by volume of a polar solvent. 5. The construction of claim I wherein the solvent system of said first layer has less than 5 percent by volume of non-polar solvent. 6. The construction of claim 1 wherein the solvent-system of said second layer has less than 5 percent by volume of polar solvent. 7. The construction of claim 5 wherein the solvent system of said second layer has less than 5 percent by volume of polar solvent. 8. The construction of claim 1 wherein a strippable carrier layer is in contact with said first layer. 9. The construction of claim 4 wherein a strippable carrier layer is in contact with said first layer. 10. The construction of claim 7 wherein a strippable carrier layer is in contact with said first layer. 11. The construction of claim 8 wherein the organic polymeric binder of said first layer comprises a phenolic resin. 12. The construction of claim 9 wherein the organic polymeric binder of said first layer comprises a phenolic resin. 13. The construction of claim 10 wherein the organic polymeric binder of said first layer comprises a phenolic resin. 14. The construction of claim 1 wherein the solvent system for said first layer comprises a polar solvent selected from the group consisting of ketone, a halogenated hydrocarbon and an ester. 15. The construction of claim 12 wherein the solvent system for said first layer comprises a polar solvent selected from the group consisting of a ketone, a halogenated hydrocarbon and an ester. 16. The construction of claim 13 wherein the solvent system for said first layer comprises a polar solvent selected from the group consisting of a ketone, a halogenated hydrocarbon and an ester. 17. The construction of claim 14 wherein the solvent system for said second layer comprises a non-polar solvent selected from the group consisting of aromatic hydrocarbons and aliphatic hydrocarbons. 18. The construction of claim 15 wherein the solvent system for said second layer comprises a non-polar solvent selected from the group consisting of aromatic hydrocarbons and aliphatic hydrocarbons. 19. The construction of claim 16 wherein the solvent system for said second layer comprises a non-polar solvent selected from the group consisting of aromatic hydrocarbons and aliphatic hydrocarbons. 20. The construction of claim 15 wherein the thermally softenable polymeric adhesive comprises an organic polymer selected from the group consisting of polyenes and acrylics and the solvent system of said second layer comprises a non-polar solven selected from the group consistin of aromatic hydrocarbons and aliphatic hydrocarbons.

Inventors: KOELSCH, PETER M. C/O MINNESOTA MINING AND, KRECH, ROGER I. C/O MINNESOTA MINING AND
Applicants: MINNESOTA MINING AND MANUFACTURING COMPANY
Application year: 1984
Main classification: G03F3
IPC codes: G03F7, G03C1, G03F3