The present invention provides a method of making a laminated structure. The method includes placing an adhesive, RF-heatable polymer blend adjacent to at least a portion of a substrate surface, and subjecting the polymer blend to RF radiation (e.g., microwave) to melt the RF heatable blend to effect bonding between the blend and the substrate. The RF- heatable polymer blend comprise (a) an ethylene/carbon monoxide (ECO) copolymer and (b) an ethylene polymer grafted with a n a,B-ethylenically unsaturated dicarboxylic acid or anhydride.

The use of high-frequency electromagnetic energy (e.g., microwave) as a means of heating is an advancing art which finds application in many fields. It would be commercially useful to use such heating means in the preparation of heat sealable laminates. Unfortunately, most olefinic polymers are not heat sealable by high-frequency heating operations because they are either not heated by high-frequency radiation (energy) or only heated slowly. In production assembly lines, a quick heat-seal is important.

There are additives (sensitizers) which can be blended into a polymer, e.g. polyethylene, to render it heatable by electromagnetic high-frequency energy, such as talc, ZnCl2 carbon black, nylon, iron oxide, and others. Such additives, however, usually have a pronounced visual, physical, or chemical effect which, in some applications, is desirably avoided. Furthermore, when using additives as sensitizers one is faced with having to obtain a uniform distribution of the "hot spots" or arcing which can give irregular results and may even damage the polymer or other parts of the laminate. In addition, there are some chemical modifications that can be made on the polymer to make it heatable. Some olefinic polymers containing polar groups, or polarizable groups, at high levels of incorporation can be heated by high-frequency energy but their heating efficiency is generally so low that they are not commercially useful. Some polymers having polar groups, e.g., chlorinated polyethylene (CPE), ethylene/vinyl acetate copolymer (EVA), polyvinylchloride (PVC), polyvinylidene chloride (PVDC), and polyamides can be radiation heated at certain frequencies of electromagnetic radiation, but not at the higher frequencies of current commercial interest.

Lancaster et al., disclose high frequency (HF) heatable or heat sealable ethylene/carbon monoxide (ECO) copolymers. See the disclosure in U. S. Patents 4,847,155; 4,787,194; 4,766,035; 4,762,731; 4,684,576; 4,678,713; 4,671,982; 4,660,354; 4,640,865, 4,601,948; and 4,600,614. It is stated, for example, in USP 4,601,948 that non-HF-heatable or non-HF-sealable polymers can be made to be HF-sealable by either incorporation of carbon monoxide by copolymerization or

by blending or grafting a carbon monoxide ^" copolymer or terpolymer into the polymer matrix. This patent additionally discloses terpolymers of ethylene, carbon monoxide and acrylic methacrylic acid which have RF- sealability and improved adhesion.

The present invention provides a method of making a laminated structure. The method includes placing an adhesive, RF-heatable polymer blend adjacent to at least a portion of a substrate surface, and subjecting the polymer blend to RF radiation (e.g., microwave) to melt the RF heatable blend to effect bonding between the blend and the substrate. The RF- heatable polymer•blend comprise (a) an ethylene/carbon monoxide (ECO) copolymer and (b) an ethylene polymer grafted with a n a,B-ethylenically unsaturated dicarboxylic acid or anhydride.

Methods of preparing ECO copolymers and terpolymers are well known, as shown by the US Patents to Lancaster et al.

Those ECO copolymers which are heatable by high-frequency electromagnetic radiation are polymers typically prepared by polymerizing ethylene and carbon monoxide, optionally with a small proportion of one or more C3-C8 aliphatic olefins or a hydrocarbyl ester of an ethylenically unsaturated organic carboxylic acid having 3 to 8 carbon atoms, or a vinyl ester of an alkanoic acid of 3 to 8 carbon atoms. Examples of such C3-C8 aliphatic olefins include propylene, butene-1, hexene-1, octene-1, and 4-methyl-pentene-1. Examples of hydrocarbyl esters and vinyl esters include methyl acrylate, ethyl acrylate, methyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate, and vinyl acetate. As used herein, the term "copolymers" includes terpolymers containing up to 20 percent by weight of one or more

termonomers in addition to ethylene and carbon monoxide (CO). Partially hydrogenated ECO copolymers are also included in the term "copolymers". U. S. Patent 2,495,292 discloses methods of hydrogenating CO groups in an ECO polymer chain to form partially hydrogenated ECO copolymers.

The ECO copolymers typically contains from about 0.5 to about 50 percent by weight CO, preferably from about 1 to about 40 weight percent CO, and more preferably from about 5 to about 30 percent CO, and more preferably from about 5 to about 30 percent by weight CO. The ECO copolymers are characterized by a melt index (I2) in the range of from abut 0.1 to about 1000 dg/min, and more preferably by an I2 of from about 0.5 to about 50 dg/min. The melt index is generally inversely related to the molecular weight of the polymer. As used herein, melt index (I2) is determined according to ASTM D-1238, condition E (190°C, 2.16 kg) unless otherwise stated.

Adhesives comprising anhydride or dicarboxylic acid grafted polymers of ethylene are prepared as ingredients of the present blends. Polymers which may be suitably grafted with dicarboxylic functionality include, for example, HDPE, LDPE, LLDPE, and ECO copolymers. Grafted ECO copolymers can alternatively be utilized in accordance with the present invention in an unblended state exhibiting novel properties similar to the polymers blends. Grafting unsaturated monomer molecules onto a- olefin polymers has been disclosed in a number of patents. The grafting technique has been used to modify the polymer properties to which the grafted molecules are attached. The following patents are representative of the prior art on grafting: U. S. Patents 2,970,129;

3,177,269; 3,270,090; 3,873,643; 3,882,194; 3,886,227; 4,087,587; 4,087,588; 4,239,830; 4,298,712; 4,394,485; U. K. Patent 2,081,726; Jap. Kokai 49(1973)-129742.

The anhydride or dicarboxylic acid groups generally comprise from about 0.02 to about 6 weight percent of the grafted ethylene polymer, preferably from about 0.1 to about 3 percent by weight, most preferably from about 0.1 to about 2 percent by weight.

The HDPE polymers which are suitable for 0 grafting are normally solid, high molecular weight polymers prepared using a coordination-type catalyst in a process wherein ethylene is homopolymerized or copolymerized with a small amount of C3 to C8 alpha- olefins for property modification. Their density range 5 is about 0.940 to about 0.965 g/cm3, but preferably from about 0.945 to about 0.960 g/cm3.

The LLDPE polymers which are suitable for grafting normally have a density in the range of about 0.88 to about 0.935 g/cm3, preferably from about 0.90 to 0 about 0.925 g/cm3. It is known to practitioners of the relevant arts that the density will depend, in large part, on the particular a-olefin(s) used as comonomer(s) and on the amount of the a-olefin(s) incorporated into ,- the copolymer. The a-olefin(s) copolymerized with ethylene to make LLDPE comprises a minor amount of at least one a-olefin(s) of from C3 to C12, most preferably from C4 to C8; 1-octene is especially preferred. The a- olefins comonomer may constitute from about 0.5 percent 0 to about 0.5 percent to about 35 percent by weight of the copolymer, preferably about 1 percent to about 20 percent by weight, most preferably from about 2 percent to about 15 percent by weight.

The LDPE polymers which are suitable for grafting are characterized as having a density in the range of from about 0.91 to about 0.93 g/cm3.

The melt index (Iio) of the grafted polymers is preferably in the range of from about 0.01 to about 1000 dg/min, more preferably in the range of from about 0.05 to 20 dg/min. The melt index (Iio) is determined according to ASTM D-1238, condition N (190°C/10.0 kg) unless otherwise indicated.

The unsaturated dicarboxylic acid and anhydride compounds suitable as graft monomers, for which maleic acid and maleic anhydride are preferred, are known. They are conjugated acids or anhydrides, in contradistinction to the fused ring and bicyclo structures of the non-conjugated unsaturated acids of, for example e.g., U. S. Patents 3,873,643 and 3,882,194. Conjugated, unsaturated dicarboxylic acids and anhydrides applicable as graft monomers include maleic acid, maleic anhydride, nadic anhydride, nadic methyl anhydride, himic anhydride, methyl himic anhydride, 7- endoxobicyclo[2.2.1]hept-5-2,3-dicarboxylic anhydride, tetrahydrophthalic anhydride, itaconic acid, and citraconic acid, but preferably maleic acid and maleic anhydride. Diacid adducts of the above anhydride monomers are acceptable as well. It is noted that fumaric acid, when heated, gives off water and rearranges to form maleic anhydride, thus is operable in the present invention. The grafting, for example, of succinic acid or succinic anhydride groups onto ethylene polymers may be done by methods described in the art, which involve reacting maleic acid or maleic anhydride in admixture with heated polymer, generally using a peroxide or free- radical initiator to expedite the grafting.

Grafting may be effected in the presence of oxygen, air, hydroperoxides or other free radical initiators, or in the essential absence of these materials when the mixture of monomer and polymer is maintained under high shear in the absence of heat. A conventional method for producing the graft copolymer is the use of extrusion machinery, however, Brabender mixers or Banbury mixers, roll mills and the like may also be used for forming the graft copolymers. We prefer to employ a twin-screw devolatilizing extruder (such as a Werner-Pfleiderer twin-screw extruder) wherein a dicarboxylic acid or anhydride thereof such as maleic acid (or maleic anhydride) is mixed and reacted with the ethylene polymer at molten temperatures, thereby producing and extruding the grafted polymer. See, for example, the method described by Strait et al. in US Patent 4,762,890. The so- produced grafted polymer is then blended, as desired, with ECO copolymer to produce the blends of this invention, such as, for example, by dry blending and/or by using conventional mixing equipment such as extruders, mixers, roll mills and the like.

The graft polymer can be blended with the ECO copolymer in substantially any proportion. Preferably, the blend comprises from about 5 to about 50 parts by weight of the grafted ethylene polymer, wherein the parts by weight of both the grafted polymer and the ECO polymer total 100. The adhesive properties of the novel polymer blends of this invention may be utilized by any convenient method in making laminate structures, such as by hot-melt application, by post-heating of the adhesive insitu on the substrate, by application of the adhesive in a carrier, such as in a solvent or as a dispersion in

an aqueous carrier or in a non-solvent. The adhesive may be used in joining substrates of similar or dissimilar materials. The polymer blends are preferably used as films which have the beneficial property of being heat sealable at high-frequencies which are in or near, the microwave range.

The polymer blends of the present invention are quite similar in optics and physical properties to the polymer constituents. 0 As used herein, the terms "high-frequency" or "RF" refers to terms electromagnetic energy frequencies of 0.1-30,000 MHz. This covers the radio frequency range (1 MHz -300 MHz) and the microwave frequency range (300 MHz-10,000 MHz) which are of particular interest 15 here, with special interest in the radio frequency range.

Uses for this technology includes packaging applications where high speed and/or non-destructive seals are required, e.g. high frequency-activated

20 adhesive films; extrusion coatings; moldings; hot melts in uses such as aseptic packaging, reactor pouches, sandwich bags, lamination of foam, fabric, or film layers; powder moldings, and the like. Furthermore, the _?c - present invention provides polymers suitable for use in RF extruders including continuous extruders or batch extruders. Wire and cable coatings can be applied in a continuous RF extruder by the present invention.

Microwave sealing applications are particularly 30 useful in making microwave-sealable plastic bags, toothpaste tubes, shampoo tubes, and valve bags.

The advantages of heating with high-frequency electromagnetic energy waves include: fast and efficient heating; the ability to heat through poor heat-conductors, e.g., paper or cardboard exteriors; favorable economics, based on efficient use of energy

input; the ability to seal, bond or laminate large surface areas; the ability to seal selected local sites without heating the entire laminate structure; and the ability to seal wet surfaces at microwave frequencies where moisture couples with the energy to provide heat for the bonding.

Sealing rates can be determined utilizing the equation found in U.S. Patent 4,601,948 to Lancaster et al.

An advantage to dicarboxylic acid functionality-containing ECO polymers and blends of the present invention, compared to the ECO polymers and blends containing interpolymerized monocarboxylic acid functionality of U. S. Patent 4,601,948 is similar adhesive strength to aluminuπ and PVDC at a greatly reduced concentration of the acid monomer. Manufacturing advantages to this include, for example, reduced material costs and greatly reduced equipment costs in comparison to the more expensive equipment generally required to process the more corrosive, higher acid-containing streams.

Examples 1-10 A maleic anhydride grafted ECO copolymer (EC0- g-MAH) was fabricated as follows:

An ECO copolymer having a melt index (I2) of 9.91 dg/min was extruded with maleic anhydride (1.54 phr) in a solution of methyl ethyl ketone (50% maleic anhydride by weight) and 2,5-dimethyl-2,5-bis(t-butyl peroxyl) hex-3-yne at a weight ratio of peroxide to anhydride of 0.03:1 using a Werner-Pfleider twin screw devoltailization extruder. The temperature profile across the extruder heat zones was 180°C, 200°C, 190°C, 165°C with a 105.8 g/min throughput. The final

incorporated concentration of maleic anhydride was 0.5% by weight (as determined by titration) with a final melt index (I ) of 1.09 dg/min.

Using a 25.4 mm extruder at an average temperature of 177°C, 1.4 kg samples of the above maleic anhydride grafted polymers were dry blended then melt blended with an ungrafted ECO copolymer to produce polymer blends. To determine the microwave sensitivity of the grafted polymers and blends thereof which embody this invention, 20 g of each sample shown below in Table I were placed in 8.9 cm diameter poly(tetrafluoro- ethylene evaporating dishes, and these were placed in a Litton Minute Master microwave oven having a frequency of 2450 Hz. A setting of "high" was used for each test and the dwell time for melting all of the pellets was recorded.

TABLE I

TIME REQUIRED TO MELT RESIN SAMPLES IN A

LITTON MINUTE MASTER MICROWAVE OVEN

Examples 11-16

In order to determine the RF-sealability of the grafted polymers and blends of the present invention (see description in Examples 1-10) a Callahan 1-1/2 KW high-frequency electronic generator equipped with a 23.8 mm x 30.5 cm brass sealing electrode and operating over a frequency range of 20-40 MHz (RF) was utilized in the following sealing experiment. Films 0.04 mm to 0.06 mm thick blown from polymer materials of Table II were irradiated using the above RF sealer at various dwell settings (seal times) and power settings. The unit was set to about 27 MHz. The seals were examined and a seal was considered to have been made when the two sheets of material could not be separated at the seal point without tearing either piece of film. Table II shows how ECO copolymers grafted with dicarboxylic acid functionality maintained their original RF sealing property and how the addition of an ungrafted ECO copolymer to an ethylene polymer grafted with dicarboxylic acid functionality such as HDPE-g-MAH which is not RF sealable acquired this property.

TABLE II RADIO FREQUENCY SEALABILITY

1 5 wt. CO, 3.22 I2-

2 11wt.% CO, 9.91 I2-

3 11 wt.% CO, 0.46 MAH, 8.0 12 (see description in Examples 1-10).

4 0.5 wt.% MAH, 1.09 12 (see description in Examples 1-10). 6 Did not melt.

The most difficult to seal polymer sample (Example 16) required only 2 seconds seal time at a 40% power setting. This sample, of course, had the smallest carbon monoxide concentration.

Examples 17-34

Films were fabricated from blends of HDPE-g-MAH and ungrafted ECO, as described in Examples 1-10, with a thickness of 0.04 mm using a Killion blown film unit with a 50.8 mm circular die and a 19 mm screw. The films were used in adhesive testing to various substrates. Adhesive tests, the results of which appear in Table III below, involved sealing a film of the polymer samples to be tested to a 0.04 mm think nylon-6 cast film using an Askco heat seal unit having 9 heated zones. The temperature profile across the heated zones was 121°C, 132°C, 143°C, 154°C, 166°C, 177°C, 188°C, 199°C, and 210°C. A laminate of the film of the polymer sample being tested and the substrate of interest was constructed so that the peel strength of the test film was recorded against zone temperature. An Instron testing apparatus measured the final peel strength at each zone temperature by peeling apart the laminate. The laminate had a top layer which was an adhesive film blown from the sample polymer blend, another layer which was a Mylar film release agent and a bottom layer which was Kraft paper (for support). The structure was sealed in the Askco unit at the indicated temperatures per zone for 6 seconds at a pressure of 0.28 MPa. Table III shows the adhesive strength of several concentrations of HDPE-g-MAH in ECO copolymers of 3 different compositions against zone temperature where nylon-6 is the test substrate. Table III shows better adhesive seals to

nylon-6 at reduced seal temperatures for ^{' "} the blended polymer than either component separately.

. an . m equvaen pee s reng orce.

Examples 35-52

Films were fabricated from blends of HDPE-g-MAH and ungrafted ECO, as described in Examples 1-10, with a thickness of 0.04 mm using the film blowing equipment described in Examples 17-34. Adhesive tests, the

,- results of which appear in Table IV below, involved sealing a film of the polymer samples to a 0.13 mm thick PVDC using an HST-09 Askco heat seal unit having 6 heated zones. The temperature profile across the heated zones was 121°C, 132°C, 143°C, 154°C, 166°C, and 177°C.

10 The last three zones were turned off due to decomposition of PVDC at temperatures above 177°C. The procedure for testing the polymer blend samples for adhesion to PVDC substrate is described in Examples 17- 34. Table IV shows better a hesive seals to PVDC at

15 reduced seal temperatures for the blended polymer than either component separately.

0

5

0

TABLE IV PEEL STRENGTH OF BLENDED HDPE-g-MAH1 IN ECO FROM SARAN ^© PVDC (N/m)

PROPORTION OF HDPE-g- ZONE TEMPERATURE (°C)

MAH ⁽ w - ^. JIN BLEND ,-, ₂ ,43 ^" w ~ ^" _. 66 177

I

I- ^** 00 I

icates film breaking prior to peeling. In these cases, the films experience etween . an .2 N/m equivalent peel strength force.

Examples 53-57

Sheets were cast from ECO-g-MAH and blends thereof with ungrafted ECO (see description in Examples 1-10) and adhesion tests performed using a wide range of substrates at room temperature according to the following procedures: On a 22.9 cm x 15.2 cm compression molder having two platens set at 177°C, and two platens water cooled, was molded a 0.64 mm plaque of material to be tested for adhesion. An appropriate amount of material to be molded was placed in the 0.64 mm mold between two sheets of Mylar, which, in turn was between two metal support plates. The support plates containing the resin and mold were placed between the 177°C platens of the compression molder and the platens were closed and allowed to heat with no pressure for one minute. After this time period, 68.9 MPa platen pressure was applied for one minute. The Mylar was removed and the polymer was cut from the mold using a razor blade against a clean, hard surface.

The molded specimen (22.9 cm x 15.2 cm) was placed against a substrate (at least 22.9 cm x 15.2 cm) with a Mylar film tab (7.6 cm x 22.9 cm) centered in traverse manner between the test specimen and substrate, leaving about 3-8 cm of the tab protruding from each side of the so-formed "sandwich." then a Mylar film (30.5 cm x 30.5 cm) placed on each side of the specimen/substrate sandwich and a steel support plate and placed against each of the Mylar films. ("Mylar" is the well-known DuPont tradename for polyethylene terephthalate. ) The sandwich structure described above was placed between the hot (177°C) platens of a compression molder and pressed immediately to 68.9 MPa and held there for two minutes. After this, the sandwich was removed from the hot platens and placed

between the cool platens for two minutes. ^' The sandwich was removed from the press and the Mylar film was removed from each side of the polymer/substrate laminate.

The laminate was then cut longitudinally into five equal 2.5 cm wide strips. Each of five test strips were peeled back slightly by hand and mounted (clamped) in the Instron tensile tester. The Instron was run at a pulling rate of 5.1 - 7.6 cm had been peeled. The average of the five peels was taken as the adhesion strength.

The following substrates were used:

1. Electrolytic chromium coated steel (ECCS) had a thickness of 0.15 mm; this steel was chosen due to it3 popular use in polyolefin applications.

2. Aluminum was coiled aluminum, 0.13 mm thick,

45.7 cm wide, grade 3003-H14.

3. The copper was copper sheet, 110 alloy, fully annealed, 99% pure, 0.13 mm thick.

4. The nylon-6 was a film 0.17 mm thick and

50.8 cm wide.

5. The oriented polypropylene (PP) film was 0.13 mm thick and 15.2 cm wide. The data from Table V indicate synergistically improved adhesion to steel, aluminum, copper and PVDC of the blended polymer samples compared to samples prepared from either component separately.

TABLE V PEEL STRENGTH OF BLENDED ECO-g-MAHl IN EC02 FROM VARIOUS SUBSTRATE MATERIALS (N/m)

PROPORTION OF HDPE-g-MAH BLEND BLEND SUBSTRATE MATERIALS

EXAMPLE

(wt. %) IN 12 DENSITY

(g/cm3)

BLEND Steel Cu Al Nylon PVDC OPP PP

53 0 4.91 0.989 612.9 175.1 420.3 22.8 ' >437.83 (100% ECO) 54 10 10.86 0.986 > 1646.2 262.7 >2101.5 21.0 >420.3 (0.05% MAH) 55 20 9.98 1.032 >2101.5 297.7 > 1891.4 21.0 >893.2 (0.09% MAH) 56 50 9.93 1.935 >2189.1 315.2 >1698.7 24.5 > 1155.8 (0.23% MAH) 57 100 8.04 0.989 > 1348.5 280.2 788.1 22.8 >788.1

(100% ECO-g- MAH)

1 11 % CO by weight, 0.46 MAH by weight, 8.04 I2 (see description in Examples 1-10). 2 11 % CO by weight, 9.91 I2. 3 > symbol indicates cohesive failure of sample or substrate at the stated test strength.

Examples 58-74

Sheets were cast from HDPE-g-MAH and blends thereof with ungrafted ECO (see description in Examples 1-10) and adhesion tests were performed on a variety of substrates at room temperature according to the procedures of examples 53-57.

The adhesive data are presented in Table VI. It must be noted form the data that those substrate materials which showed good adhesive peel strength with films of HDPE-g-MAH blended with ECO, the blended polymer films materially failed at lower peel strengths than measurably achieved for the component HDPE-g-MAH alone which suffered adhesion failure.

TABLE VI PEEL STRENGTH OF BLENDED HDPE-g-MAHl IN ECO FROM VARIOUS SUBSTRATE MATERIALS (N/m)

ECO

SUBSTRATE MATERIALS

I IN) J I

(100% HDPE-g-MAH)

69 15 1.85 0.961 0 0.7 0.5 0 52.5 0 17.5

(100% ECO)

70 15 1.85 1.67 0.982 20 71 15 1.85 1.70 0.979 25 72 15 1.85 1.71 0.977 30 73 15 1.85 1.60 0.971 50 74 1.01 0.950 100

(100% HDPE-g-MAH)

1 0.50 weight percent MAH, 1.09 I2 (see description in Examples 1 -10).

2 CF (cohesive failure) indicates breaking of the sample sheet prior to peeling. In these cases, the polymer experienced between 350.2 and 1576.1 N/m of equivalent peel strength force. The blended materials - -

The foregoing description of the invention is illustrative and various modifications will become apparent to those skilled in the art in view thereof. It is intended that all such variations which fall within the scope and spirit of the appended claims be embraced thereby.