Multilayered structure with water-impermeable substrate

• US 9,573,349 B1
• Filed: 07/30/2015
• Issued: 02/21/2017
• Est. Priority Date: 07/30/2015
• Status: Active Grant

• Current Assignee: Eastman Kodak Company
• Original Assignee: Eastman Kodak Company
• Inventors: Dannhauser, Thomas Joseph, Bugner, Douglas Eugene, Putnam, David D., Lindstrom, Brian L
• Primary Examiner(s): Shewareged, Betelhem
• Application Number:
  US14/813,491
• Publication Number:
  US 20170028688A1
• Time in Patent Office: 572 Days
• US Class Current: 1/1
• CPC Class Codes: B32B 2250/24 All layers being polymeric
• CPC Class Codes: B32B 2255/10 on synthetic resin layer or on natural or synthetic rubber layer
• CPC Class Codes: B32B 2255/26 Polymeric coating
• CPC Class Codes: B32B 2307/4026 within the layer by addition of a colorant, e.g. pigments, dyes
• CPC Class Codes: B32B 2307/41 Opaque
• CPC Class Codes: B32B 2307/412 Transparent
• CPC Class Codes: B32B 2307/75 Printability
• CPC Class Codes: B32B 27/08 of synthetic resin
• CPC Class Codes: B32B 27/32 comprising polyolefins comprising vinyl (co)polymers or acrylic (co)polymers B32B27/30
• CPC Class Codes: B32B 27/36 comprising polyesters
• CPC Class Codes: B32B 27/40 comprising polyurethanes
• CPC Class Codes: B32B 7/12 using interposed adhesives or interposed materials with bonding properties
• CPC Class Codes: B41M 3/008 Sequential or multiple printing, e.g. on previously printed background; Mirror printing; Recto-verso printing; using a combination of different printing techniques; Printing of patterns visible in reflection and by transparency; by superposing printed artifacts
• CPC Class Codes: B41M 5/0011 Pre-treatment or treatment during printing of the recording material, e.g. heating, irradiating after-treatment of prints B41M7/00; printers for treating or overcoating copy materials before, during or after printing B41J11/0015
• CPC Class Codes: B41M 5/0017 Application of ink-fixing material, e.g. mordant, precipitating agent, on the substrate prior to printing, e.g. by ink-jet printing, coating or spraying
• CPC Class Codes: B41M 5/0047 by ink-jet printing
• CPC Class Codes: B41M 5/0064 on plastics, horn, rubber, or other organic polymers
• CPC Class Codes: B41M 5/502 characterised by structural details, e.g. multilayer materials supports, backcoats or intermediate layers for thermal dye transfer donor and receiver sheets B41M5/41, B41M5/42
• CPC Class Codes: B41M 5/506 Intermediate layers
• CPC Class Codes: B41M 5/508 Supports
• CPC Class Codes: B41M 5/5218 : characterised by inorganic additives, e.g. pigments, clays
• CPC Class Codes: B41M 5/5236 : characterised by the use of natural gums, of proteins, e.g. gelatins, or of macromolecular carbohydrates, e.g. cellulose
• CPC Class Codes: B41M 5/5245 : characterised by the use of polymers containing cationic or anionic groups, e.g. mordants
• CPC Class Codes: B41M 5/5254 : characterised by the use of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
• CPC Class Codes: B41M 7/0027 : using protective coatings or layers by lamination or by fusion of the coatings or layers
• CPC Class Codes: B41M 7/0036 : using protective coatings or layers dried without curing
• CPC Class Codes: B41M 7/0045 : using protective coatings or film forming compositions cured by mechanical wave energy, e.g. ultrasonics, cured by electromagnetic radiation or waves, e.g. ultraviolet radiation, electron beams, or cured by magnetic or electric fields, e.g. electric discharge, plasma
• CPC Class Codes: B41M 7/0054 : using protective coatings or film forming compositions cured by thermal means, e.g. infrared radiation, heat
• CPC Class Codes: C08L 29/04 : Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
• CPC Class Codes: C08L 33/14 : of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
• CPC Class Codes: C09D 11/30 : Inkjet printing inks
• CPC Class Codes: C09J 175/04 : Polyurethanes

Abstract

In accordance with the present invention, there is provided a multi-layered structure includes:

• • a) a water-impermeable substrate;
  • b) a first layer on at least one surface of the substrate comprising a water-based tie-layer composition;
  • c) a second layer formed over the first layer, wherein the second layer is a water-based ink-receptive composition includes:
    • i) a multivalent metal salt; and
    • ii) a hydrophilic binder polymer;
  • d) a third layer including at least one water-based ink composition deposited in a single pass by an inkjet printing process, wherein the water-based ink composition includes an anionically stabilized, water-dispersible pigment; and
  • e) additional layers deposited over the one or more ink layers and exposed second layer, the additional layers selected from one or more of the following compositions:
    • i) an opaque white layer;
    • ii) a protective layer; and
    • iii) an adhesive layer, further includes a continuous protective plastic or paper layer adhered thereto.

Claims

1. A multilayered structure comprising:

a) a water-impermeable substrate;

b) a first layer on at least one surface of the substrate comprising a water-based tie-layer composition;

c) a second layer formed over the first layer, wherein the second layer is a water-based ink-receptive composition comprising;

i) a multivalent metal salt; and

ii) a hydrophilic binder polymer;

d) a third layer including at least one water-based ink composition deposited in a single pass by an inkjet printing process, wherein the water-based ink composition comprises an anionically stabilized, water-dispersible pigment; and

e) additional water-based layers deposited over the one or more ink layers and exposed second layer, the additional layers selected from one or more of the following compositions;

i) an opaque white layer;

ii) a protective layer; and

iii) an adhesive layer, further comprising a continuous protective plastic or paper layer adhered thereto,

wherein the dry coverage of the second layer is less than 1.5 g/m².

2. The multilayered structure of claim 1, wherein the water-impermeable substrate is selected from polyesters, polyimides, polycarbonates, polystyrenes, polyolefins, polyurethanes, polyvinyl acetates, polyvinyl chlorides, polyvinylidene chlorides, and copolymers, mixtures, co-extrudates, or laminates thereof.

3. The multilayered structure of claim 1, wherein the water-based tie-layer comprises polyvinyl alcohol, polyvinyl amine, gelatin, poly(ethyleneimine), epoxy resins, polyurethane, polyacrylamide, and derivatives, copolymers, and blends thereof.

4. The multilayered structure of claim 1, wherein the water-based tie-layer comprises a polymer or copolymer comprising 50 to 100 mole percent of glycidyl acrylate or glycidyl methacrylate monomers.

5. The multilayered structure of claim 1, wherein the water-based tie-layer comprises two sub layers, the first water-based tie-sub-layer comprising poly(ethyleneimine) and epoxy resins modified with an acidified aminoethylated vinyl polymer, and a second water-based tie-sub-layer, which is applied on top of the first sub-layer, is a cross-linked poly(vinyl alcohol) polymer.

6. The multilayered structure of claim 1, wherein the multivalent metal salt is a calcium or magnesium salt and the hydrophilic polymer binder is a cross-linked poly(vinyl alcohol).

7. The multilayered structure of claim 1, wherein the water-based ink composition comprises less than 10 wt % water miscible co-solvent.

8. The multilayered structure of claim 1, wherein the anionically stabilized, water-dispersible pigment is dispersed with an anionic polymer comprising carboxylate functionality.

9. The multilayered structure of claim 1, wherein the opaque white layer composition is a water-based white flexographic ink.

10. The multilayered structure of claim 1, wherein the opaque white layer composition is a water based white inkjet ink.

11. The multilayered structure of claim 1, wherein the protective layer composition is a water-based polyurethane.

12. The multilayered structure of claim 1, wherein the adhesive layer composition is a solventless two-part water-based polyurethane resin with an epoxy resin cross linker applied in combination with a second water-impermeable substrate.

13. The multilayered structure of claim 12, wherein the second water-impermeable substrate is selected from polyesters, polyimides, polycarbonates, polystyrenes, polyolefins, polyurethanes, polyvinyl acetates, polyvinyl chlorides, polyvinylidene chlorides, and copolymers, mixtures, co-extrudates, or laminates thereof.

14. The multilayered structure of claim 9 further comprising the protective layer composition wherein the protective layer composition is a water-based polyurethane.

15. The multilayered structure of claim 9 further comprising the adhesive layer composition wherein the adhesive layer composition is a solventless two-part water-based polyurethane resin with an epoxy resin cross linker applied in combination with a second water-impermeable substrate.

16. The multilayered structure of claim 12, wherein the lamination bond strength is >

1.0 N/cm.

17. The multilayered structure of claim 12, wherein the lamination bond strength is >

1.5 N/cm.

18. The multilayered structure of claim 1, wherein the second layer comprises between 0.05 g/m² and 1.0 g/m² of the hydrophilic binder polymer, and the weight ratio of the multivalent metal salt to the hydrophilic binder polymer is between 2.5:

1 and 0.75;

1.