Laminate structure including a primer coating therein

Abstract

A laminate structure is provided which includes a first polymeric substrate laminated to a second polymeric substrate. A primer coating comprising the reaction product of polyethyleneimine and formaldehyde is included on the surface of the first polymeric substrate which is subsequently printed with an ink or toner image prior to lamination to the second polymeric substrate. The primer coating provides good toner and/or ink adhesion to the polymeric substrate. The primer coating also provides improved bond strength upon lamination of the first and second polymeric substrates as well as providing water resistance to the laminate structure.

Claims

1. A laminate structure comprising first and second polymeric substrates each having first and second major surfaces, wherein at least one major surface of said first polymeric substrate includes a primer coating thereon formed from a primer composition consisting of polyethyleneimine, formaldehyde, and water; wherein the primer composition is applied to said first polymeric substrate and dried to form the primer coating, wherein the primer coating is the reaction product of polyethyleneimine and formaldehyde, and a toner or ink image printed on said first polymeric substrate over said primer coating; and wherein said first polymeric substrate is laminated to said second polymeric substrate at the at least one major surface including said primer coating and said toner or ink image.

2. The laminate structure of claim 1 further including a laminating adhesive over the toner or ink image.

3. The laminate structure of claim 1 wherein said first and second polymeric substrates are selected from polyethylene, biaxially oriented polyethylene terephthalate (BOPET), biaxially oriented polypropylene (BOPP), cast polypropylene (CPP), coextruded polypropylene (COPP), biaxially oriented nylon (BON), and biaxially oriented polyamide (BOPA).

4. The laminate structure of claim 3 wherein said first polymeric substrate comprises BOPET and said second polymeric substrate comprises polyethylene or cast polypropylene.

5. The laminate structure of claim 3 wherein said first polymeric substrate comprises BOPA and said second polymeric substrate comprises polyethylene or cast polypropylene.

6. The laminate structure of claim 1 wherein said first polymeric substrate comprises BOPP and said second polymeric substrate comprises polyethylene, BOPP, or a BOPET metallized film.

7. The laminate structure of claim 3 wherein said first polymeric substrate comprises BOPET and said second polymeric substrate is a multilayer film comprising BOPET and one of polyethylene or cast polypropylene.

8. The laminate structure of claim 1 wherein said first polymeric substrate comprises BOPET and said second polymeric substrate comprises a multilayer film comprising metallized BOPET and one of polyethylene or cast polypropylene.

9. The laminate structure of claim 1 wherein said first polymeric substrate comprises BOPET and said second polymeric substrate comprises a multilayer substrate comprising aluminum foil and one of polyethylene or cast polypropylene.

10. A coated polymeric substrate comprising a polymeric substrate having first and second major surfaces, wherein at least one major surface of said polymeric substrate includes a primer coating thereon formed from a primer composition consisting of polyethyleneimine, formaldehyde, and water; wherein the primer composition is applied to said first major surface of said polymeric substrate and dried to form the primer coating, wherein the primer coating is the reaction product of polyethyleneimine and formaldehyde, and a toner or ink image printed on said polymeric substrate over said primer coating.

11. A laminate structure comprising first and second polymeric substrates each having first and second major surfaces, wherein at least one major surface of said first polymeric substrate includes a primer coating thereon formed from a primer composition consisting of polyethyleneimine, formaldehyde, and water; wherein the primer composition is applied to said first polymeric substrate dried to form the primer coating, wherein the primer coating is a crosslinked polyethyleneimine resin, and a toner or ink image printed on said first polymeric substrate over said primer coating; wherein said first polymeric substrate is laminated to said second polymeric substrate at the at least one major surface including said primer coating and said toner or ink image; and wherein amine groups in said polyethyleneimine react with acid groups in said toner or ink to increase the bond strength of said laminate.

12. The laminate structure of claim 11 further including a laminating adhesive over the toner or ink image.

13. The laminate structure of claim 11 wherein said first and second polymeric substrates are selected from polyethylene, biaxially oriented polyethylene terephthalate (BOPET), biaxially oriented polypropylene (BOPP), cast polypropylene (CPP), coextruded polypropylene (COPP), biaxially oriented nylon (BON), and biaxially oriented polyamide (BOPA).

14. The laminate structure of claim 13 wherein said first polymeric substrate comprises BOPET or BOPA and said second polymeric substrate comprises polyethylene or cast polypropylene.

15. The laminate structure of claim 11 wherein said first polymeric substrate comprises BOPP and said second polymeric substrate comprises polyethylene, BOPP, or a BOPET metallized film.

16. The laminate structure of claim 11 wherein said first polymeric substrate comprises BOPET and said second polymeric substrate is one of a multilayer film comprising BOPET and polyethylene, a multilayer film comprising metallized BOPET and polyethylene, and a multilayer film comprising aluminum foil and one of polyethylene, or cast polypropylene.

17. A coated polymeric substrate comprising a polymeric substrate having first and second major surfaces, wherein at least one major surface of said polymeric substrate includes a primer coating thereon formed from a primer composition consisting of polyethyleneimine, formaldehyde, and water; wherein the primer composition is applied to said first polymeric substrate and dried to form the primer coating, wherein the primer coating is a crosslinked polyethyleneimine resin, and a toner or ink image printed on said polymeric substrate over said primer coating, and wherein amine groups in said polyethyleneimine react with acid groups in said toner or ink to increase the bond strength of said laminate.

18. A laminate structure comprising: a first polymeric substrate having first and second major surfaces, wherein at least one major surface of said first polymeric substrate includes a primer coating thereon formed from a primer compositision consisting of polyethyleneimine, formaldehyde, and water; wherein the primer composition is applied to said first polymeric substrate and dried to form the primer coating, wherein the primer coating is a crosslinked polyethyleneimine resin, and a toner or ink image printed on said first polymeric substrate over said primer coating; and a second polymeric substrate laminated to at the at least one major surface of the first polymeric substrate which includes the primer coating and the toner or ink image.

19. The laminate structure of claim 18 including a laminating adhesive over the toner or ink image.

20. The laminate structure of claim 18 wherein the first polymeric substrate and the second polymeric substrate are selected from polyethylene, biaxially oriented polyethylene terephthalate (BOPET), biaxially oriented polypropylene (BOPP), cast polypropylene (CPP), coextruded polypropylene (COPP), biaxially oriented nylon (BON), and biaxially oriented polyamide (BOPA).

21. The laminate structure of claim 20 wherein the first polymeric substrate comprises BOPET or BOPA and the second polymeric substrate comprises polyethylene or cast polypropylene.

22. The laminate structure of claim 18 wherein the first polymeric substrate comprises BOPP and the second polymeric substrate comprises polyethylene, BOPP, or a BOPET metalized film.

23. The laminate structure of claim 18 wherein the first polymeric substrate comprises BOPET and the second polymeric substrate is a multilayer film comprising one of BOPET, metalized BOPET, or aluminum foil, and one of polyethylene, or cast polypropylene.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a schematic illustration of a laminate structure formed in accordance with an embodiment of the invention;

(2) FIG. 2 is a graph illustrating the bond strength of BOPET/PE laminate structures formed in accordance with an embodiment of the invention;

(3) FIG. 3 is a graph illustrating the bond strength of BOPET/PE laminate structures formed in accordance with another embodiment of the invention;

(4) FIG. 4 is a graph illustrating the bond strength of BOPET/PE laminate structures formed in accordance with another embodiment of the invention;

(5) FIG. 5 is a graph illustrating the bond strength of BOPP/BOPP laminate structures formed in accordance with another embodiment of the invention;

(6) FIG. 6 is a graph illustrating the bond strength of BOPET/Al-PE laminate structures formed in accordance with another embodiment of the invention; and

(7) FIG. 7 is a graph illustrating the bond strength of BOPP/Metallized BOPP laminate structures formed in accordance with another embodiment of the invention.

DETAILED DESCRIPTION

(8) Embodiments of the laminate structure comprising first and second polymeric substrates including a primer coating thereon as described herein provide improved toner and/or ink adhesion to polymeric substrates. While the invention has been described herein with regard to laminate structures, it should be appreciated that the primer coating may also be applied to polymeric substrates which are subsequently printed but not laminated to take advantage of the enhanced toner/ink adhesion properties provided by the primer.

(9) The primer coating improves ink or toner adhesion for a variety of printing methods and equipment, but especially improves ink or toner adhesion to polymeric substrates which are printed using high speed digital presses such as the HP Indigo WS 6000 series of digital presses or the HP 20000 or 30000 wide format digital presses. By high speed, we mean a press having a linear speed up to about 30 meters/min. for a four-color mode, and about 60 meters/min. for a two-color mode. By wide format it is meant that the printers print at a width of 29 to 30 inches (73 to 76 cm). For example, the primer coating used on the polymeric substrates comprising the laminate structure may be applied to substrates which are printed using liquid toners and/or inks suitable for HP Indigo WS6600 or WS6000, 20000 or 30000 Digital Presses. These presses are designed to print substrates used for flexible packaging. Such digital presses also include an optional in-line priming unit which applies primer to uncoated substrates in-line (following a corona treatment) and dries the primer just prior to printing. Thus, the presses are capable of priming and printing substrates in a single pass. Alternatively, the primer coating may be applied to a substrate off-line by conventional flexographic, gravure, or rod coating techniques.

(10) We have unexpectedly found that the bond strength upon lamination of a primed and printed first polymeric substrate to a second substrate is improved even though the primer coating is not present at the surface of the bond, i.e., the primer coated surface is overprinted with ink or toner and then optionally coated with a laminating adhesive. While not wishing to be bound by theory, it is believed that the increased bond strength is obtained as a result of a reaction which occurs between the components in the ink and the primer. The ink components are believed to react with the primer components by an acid-base reaction, where the base function is provided from the amine groups present in the polyethyleneimine chain, and the acid function is provided from the ink (such as HP Indigo inks which are used in the presses described herein).

(11) It has also been found that use of the primer as described herein provides a laminate having improved resistance to heated water infiltration upon immersion of the laminate. For example, when the laminates are used in retort packaging applications, the final packaging may be subjected to immersion in hot water to heat the contents of the package.

(12) Unless otherwise indicated, the disclosure of any ranges in the specification and claims are to be understood as including the range itself and also anything subsumed therein, as well as endpoints.

(13) One embodiment of the primer coating for use on the polymeric substrates forming the laminate structure comprises from about 5 to 20% by weight of polyethyleneimine, from about 0.5 to 5.0% formaldehyde, and the balance deionized water. The polyethyleneimine is preferably supplied in the form of an aqueous solution containing about 50% by weight of the polyethyleneimine but may comprise from 20 to 99 wt %.

(14) A suitable polyethyleneimine solution for use in the primer composition is commercially available from BASF under the designation Polymin P or Lupasol P. Other suitable grades of Polymin polyethyleneimines include Polymin FG, WF, G20, G35, G100, HF, PS, SK, and SNA. Other polyethyleneimines are available from Nippon Shokubai under the designation EPOMIN and include EPOMIN SP-003, SP-006, SP-012, SP-018, SP-200, SP-110, SP-1000, P-1000, P-1010, and P1050.

(15) The polyethyleneimine acts as an adhesion promoter to achieve good adhesion of the toner and/or ink image to the polymeric substrate. The polyethyleneimine is modified with formaldehyde in water, i.e., the formaldehyde acts to crosslink the polyethyleneimine chains via an aldehyde-ammonia reaction to form a resin which, upon drying, forms a film on the substrates which are coated. It should be appreciated that there are no other components present in the primer composition which could react with the polyethyleneimine other than formaldehyde.

(16) The modified polyethyleneimine renders the primer more water resistant, and consequently, the final laminate structure is water resistant, for example, when subjected to hot water immersion.

(17) The primer coating may further comprise from 0.05 to about 0.1% by weight of a wetting agent, and anti-foaming additives in an amount of from 0.05 to 0.2% by weight.

(18) The primer coating is preferably prepared by adding the polyethyleneimine and formaldehyde to water in a mixing vessel at ambient temperatures. The polyethyleneimine and formaldehyde components react to form a polymer which is known under the designation aziridine, formaldehyde resin (CAS No. 25549-69-3). When the solution of this polymer in water is applied to the surface of a substrate, the water evaporates upon drying to form a film.

(19) The primer coating may be applied to polymeric substrates including polyethylene, biaxially oriented polyethylene terephthalate (BOPET), cast polypropylene (CPP), biaxially oriented polypropylene (BOPP), coextruded polypropylene (COPP), biaxially oriented nylon (BON), biaxially oriented polyamide (BOPA), and any of the above polymers including a metallized coating thereon. The polymeric substrates may range in thickness from about 10 to about 50 m. The primer is applied to at least one major surface of the substrate which is to receive the toner/ink. Before the primer is applied, the surface of the substrate is preferably treated to ensure that the primer will wet out the surface of the film. The film is preferably treated using conventional techniques such as a flame or corona discharge treatment.

(20) The primer coating is preferably applied as an aqueous solution to at least one major surface of the substrate to form a substantially continuous coating on the surface of the substrate followed by drying the coating. The primer may be applied either inline or offline. For example, the primer may be applied in-line on a press which is fitted with an in-line priming unit. Alternatively, the primer coating may be applied in an offline process using any of a number of known techniques, including gravure or rod coating or flexographic printing. The primer composition is preferably applied to the substrate such that when dried, it forms a substantially continuous film coating having a coat weight of about 0.15 to 0.3 g/m.sup.2 (resulting in a thickness of from about 0.15 to 0.2 m).

(21) After the primer coating is applied, it may be dried to a substantially continuous, clear, adherent film by hot air, radiant heat or any other suitable means.

(22) After the primer has dried, the primer coated polymer substrate may then be printed using a digital press as described above using liquid or dry toner or ink. The printed images may take the form of graphic images, words, symbols, or any combination thereof and may cover substantially the entire surface of the substrate or be limited to one or more desired areas thereof.

(23) The primed and printed polymeric substrate is then laminated to a second polymeric substrate. The second substrate may comprise any of the above substrates and may also include multilayer substrates such as aluminum-polyethylene. A lamination adhesive may be applied to the first (primed and printed) substrate surface or to the second polymeric substrate surface prior to lamination. In some embodiments, the second substrate may be corona treated prior to application of the lamination adhesive.

(24) The lamination adhesive may be applied, for example, using a solventless type laminating machine. The adhesive may be applied at a coat weight of from about 1.8 g/m.sup.2 to about 2.2 g/m.sup.2, and preferably about 2.0 g/m.sup.2. Suitable laminating adhesives for use are solvent-free adhesives commercially available from Morchem, Sun Chemical, Henkel, Rohm and Haas, or Bostik. While solvent-free adhesives are preferred for use, it is also possible to use solvent-based adhesives or water-based adhesives. Where solvent-based adhesives are used, the adhesive is preferably applied at a coat weight of about 2.0 to 2.5 g/m.sup.2. Where water-based adhesives are used, the adhesive is preferably applied at a coat weight of from 1.5 to 2.0 g/m.sup.2.

(25) Preferred laminate structures formed in accordance with embodiments of the invention include a primed/printed biaxially oriented polyethylene terephthalate (BOPET) substrate laminated to a polyethylene substrate, and a primed/printed biaxially oriented polypropylene laminated to a (second) biaxially oriented polypropylene substrate.

(26) Other possible laminate structures include a primed/printed BOPET film laminated to polyethylene or cast polypropylene, or a primed/printed biaxially oriented polyamide (BOPA) film laminated to polyethylene or cast polypropylene. A primed/printed BOPP film may be laminated to polyethylene, a second BOPP film, or a BOPET metallized film.

(27) Other possible multilayer laminate structures include a primed/printed BOPET film laminated to a multilayer film comprising BOPET and polyethylene or cast polypropylene, or a primed/printed BOPET film laminated to a multilayer film comprising metallized BOPET and polyethylene or cast polypropylene, or a primed/printed BOPET film laminated to a multilayer substrate comprising aluminum foil and polyethylene or cast polypropylene. In all of the above laminates, BOPA primed/printed films may be used in place of BOPET.

(28) Referring now to FIG. 1, a laminate structure 10 in accordance with an embodiment of the invention is schematically shown and includes a first polymeric substrate 12 which has been coated with a primer 14 on one major surface of the substrate. Liquid toner/ink 16 is printed onto primer 14 and dried. A laminating adhesive 18 is supplied over the printed substrate, and a second polymeric substrate 20 is adhered to the laminating adhesive. As will be appreciated, additional polymeric and/or metallic layers may also be present in the overall laminate structure.

(29) The primed and printed laminate structures may be used in a number of packaging applications including stand-up pouches, flat bags, and blisters and strip packs.

(30) In order that the invention may be more readily understood, reference is made to the following example, which is intended to illustrate the invention, but is not to be taken as limiting the scope thereof.

EXAMPLE 1

(31) The following primer compositions were prepared by combining the following components at ambient temperature:

(32) TABLE-US-00001 TABLE 1 Primer A Primer B Component Weight % Weight % Polyethyleneimine.sup.1 8.6 18.0 Formaldehyde (37.5%) 1.9 2.72 Water 89.5 79.28 .sup.1Polymin P from BASF

(33) Primer A had a solids content of 5% and Primer B had a solids content of 10% (based on the total weight of the primer composition). Both compositions had a pH between about 10 and 12.

(34) The primers were applied to various film substrates (following a corona treatment) including biaxially oriented polyethylene terephthalate, polyethylene, and biaxially oriented polypropylene films. Selected primed substrates were printed with an HP Indigo WS6600 and HP 20000 press using an approved liquid toner composition with a specific image consisting of a series of 24 patches having different colors and toner coverage ranging from 100% to 350%, where toner coverage is specified as a percentage using 100% of each process color (cyan, magenta, yellow, black and white). The total coverage depends on a number of parameters including the printing process, type of substrate, the press speed, and how many colors are printed simultaneously.

(35) Laminate constructions were then formed by adhering the primed and printed substrates to a second polymeric film substrate comprising either polyethylene (PE), biaxially oriented polypropylene (BOPP), or a multilayer substrate comprising aluminum/polyethylene. The resulting laminate structures comprised BOPET/PE, BOPP/BOPP, and BOPET/Al-PE, where the PET film had a thickness of 12 m, the BOPP film had a thickness of 20 m, the PE film had a thickness of 90 m, and the Al-PE film had a thickness of 8 m (aluminum) and 90 m (PE). A BOPP/metallized BOPP structure was also formed having a thickness of 30 m.

(36) The substrates were adhered using solventless or solvent-based lamination adhesives as described below. Prior to application of the lamination adhesive, the second polymeric substrates were corona treated. The lamination adhesives were then applied using a Nordmeccanica labo combi 400 laminating machine.

(37) Lamination was also performed using a Nordmeccanica Labo Combi 400 laminating machine. The lamination bond strength of the laminated structures was then determined using the procedure described in ASTM F88. This is a peel test which determines the seal strength of the package, which is defined as the measure of the ability of a package seal to resist separation. The test indicates package integrity as well as the ability of the lamination process to produce consistent seals. A testing technique was used in which a tail of each specimen was secured in opposing grips and the seal was hand-supported at a 90 perpendicular angle to the tails while the test was conducted. Strips of one inch in width were used for measurements. After initiating delamination between the relevant film plies, the average force required to peel the two legs of the test pieces was recorded.

(38) Table 2 below illustrates the failure modes observed upon peeling the substrates apart.

(39) TABLE-US-00002 TABLE 2 Tear (Film Tear) NT (Non Transfer) PT (Partial Transfer) TT (Total Transfer) Film tear is observed Upon peeling, ink Upon peeling, part of Upon peeling, all during peeling of layer remains on the the ink layer remains ink layers remain either the first or first polymeric on the first polymeric on the second second substrate substrate substrate and splits to polymeric substrate the second polymeric substrate

(40) FIG. 2 illustrates the lamination bond strength and failure mode for a biaxially oriented polyethylene terephthalate/polyethylene (BOPET/PE) laminate in which BOPET was coated with Primer B, printed, and adhered to the PE substrate with a solventless adhesive (PL 272A/CF72 from Morchem). The primer was applied at coat weights of 0.13, 0.17, and 0.23 gsm. As can be seen, for substrates having ink coverage of 100-200%, the lamination bond strength is greater than 3.5 N/inch.

(41) FIG. 3 illustrates the lamination bond strength and failure modes for a biaxially oriented polyethylene terephthate/polyethylene laminate (BOPET/PE) in which the BOPET film was coated with Primer B, printed (ink coverage of 350%) and adhered to the PE film with a solventless adhesive (DICDRY NS 2100A/HA 210B from DIC Corporation). This adhesive is preferably prepared at a ratio of 100/140 for components A/B in order to obtain optimum lamination bond strength values. The primer was applied at coat weights of 0.1, 018, 0.23, and 0.3 gsm. As can be seen, at higher coat weights, the lamination bond strength remains high 80 days after lamination.

(42) FIG. 4 illustrates the lamination bond strength and failure modes for a biaxially oriented polyethylene terephthate/polyethylene laminate (BOPET/PE) in which the PET film was coated with Primer B, printed, and adhered to the PE film with a solvent-based adhesive (PS 246A/CS90 from Morchem). The primer was printed at coat weights of 0.13 gsm, 0.17 gsm, and 0.23 gsm and the bond strength was measured seven days after lamination.

(43) FIG. 5 illustrates the lamination bond strength and failure modes for a biaxially oriented polypropylene/biaxially oriented polypropylene (BOPP/BOPP) laminate in which the first BOPP film was coated with Primer B, printed (350% ink coverage), and adhered to the second BOPP film with a solventless adhesive (PL 272A/CF72 from Morchem). The primer was printed at a coat weight of 0.18 gsm.

(44) FIG. 6 illustrates the lamination bond strength and failure modes for a biaxially oriented polyethylene terephthalate/aluminum-polyethylene (BOPET/Al-PE) laminate in which the BOPET film was coated with Primer B, printed (350% ink coverage), and adhered to the Al-PE film with a solventless adhesive (DICDRY NS 2100A/HA 210B from DIC Corporation). The primer was printed at a coat weight of 0.18 gsm.

(45) FIG. 7 illustrates the lamination bond strength and failure modes for a biaxially oriented polypropylene/metallized biaxially oriented polypropylene laminate (BOPP/met-BOPP) in which the BOPP film was coated with Primer B, printed (350% ink coverage), and adhered to the metallized BOPP film with a solventless adhesive (DICDRY NS 2100A/HA 210B from DIC Corporation).

EXAMPLE 2

(46) The primer compositions of Example 1 and a separate coating of neat polyethyleneimine were applied to a first polymeric substrate (BOPET or BOPP) and then laminated to a second polymeric substrate (polyethyene) without the application of a laminating adhesive. The substrates were laminated at a heat seal temperature of 135 C. using heated metal jaws at a pressure of 40 PSI for 1.5 seconds.

(47) The formed laminates were then subjected to a peel test pursuant to ASTM F88 with and without being subjected to immersion in water and alcohol at room temperature. The results are shown below in Tables 3-6.

(48) TABLE-US-00003 TABLE 3 BOPET/PE laminate (Primer coat weight 0.2 g/m.sup.2) Bond strength (N/inch) Polyethylene imine Primer (neat) Primer A Primer B No immersion 5.75 6.22 5.32 1 hour immersion in 0.02 0.28 0.03 water 1 hour immersion in 0.019 1.9 1.36 isopropylic alcohol

(49) TABLE-US-00004 TABLE 4 BOPET/PE laminate (Primer coat weight 0.05 g/m.sup.2) Bond strength (N/inch) Polyethylene imine Primer (neat) Primer A Primer B 1 hour immersion in 0.08 0.41 0.42 water

(50) TABLE-US-00005 TABLE 5 BOPP/PE laminate (Primer coat weight 0.2 g/m.sup.2) Bond strength (N/inch) Polyethylene imine Primer (neat) Primer A Primer B No immersion 7.89 8.72 7.78 1 hour immersion in 0.02 1.85 0.061 water

(51) TABLE-US-00006 TABLE 6 BOPP/PE laminate (Primer coat weight 0.05 g/m.sup.2) Bond strength (N/inch) Polyethylene imine Primer (neat) Primer A Primer B No immersion 7.46 7.28 8.22 1 hour immersion in 1.54 8.55 2.91 water

(52) As can be seen, the laminates including the primer compositions of the invention exhibited higher bond strength after immersion than the substrates/laminates which were treated with PEI alone.

(53) Having described the invention in detail and by reference to preferred embodiments thereof, it will be apparent that modifications and variations are possible without departing from the scope of the invention.