CA1200041A - Adhesive blends and composite structures - Google Patents

Adhesive blends and composite structures

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Publication number
CA1200041A
CA1200041A CA000415153A CA415153A CA1200041A CA 1200041 A CA1200041 A CA 1200041A CA 000415153 A CA000415153 A CA 000415153A CA 415153 A CA415153 A CA 415153A CA 1200041 A CA1200041 A CA 1200041A
Authority
CA
Canada
Prior art keywords
blend
composite
adhesive
ethylene
substrate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
CA000415153A
Other languages
French (fr)
Inventor
Ashok M. Adur
Seymour Schmukler
John Machonis, Jr.
Mitsuzo Shida
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Equistar Chemicals LP
Original Assignee
Norchem Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to US33998482A priority Critical
Priority to US339,984 priority
Application filed by Norchem Inc filed Critical Norchem Inc
Application granted granted Critical
Publication of CA1200041A publication Critical patent/CA1200041A/en
Expired legal-status Critical Current

Links

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04Interconnection of layers
    • B32B7/12Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/04Layered products comprising a layer of synthetic resin as impregnant, bonding, or embedding substance
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/06Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/32Layered products comprising a layer of synthetic resin comprising polyolefins
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/32Layered products comprising a layer of synthetic resin comprising polyolefins
    • B32B27/322Layered products comprising a layer of synthetic resin comprising polyolefins comprising halogenated polyolefins, e.g. PTFE
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIAL AS ADHESIVES
    • C09J123/00Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/04Homopolymers or copolymers of ethene
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIAL AS ADHESIVES
    • C09J123/00Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/18Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIAL AS ADHESIVES
    • C09J151/00Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/06Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/04Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof

Abstract

Abstract Resin blends that are strong adhesives to var-ious substrates and especially to polar substrates.
These blends comprise (a) a graft copolymer of a poly-ethylene backbone grafted with at least one grafting monomer comprising one or more polymerizable ethylen-ically unsaturated carboxylic acids or acid derivatives such as acid anhydrides, acid esters, salts, amides, imides, and the like, (b) a LDPE, a linear low density polyethylene, or an ethylene-unsaturated ester copol-ymer and (c) a poly(.alpha.-olefin).
The disclosure also includes composite struc-tures comprising one or more substrates and a blend of the above as the adhesive in contact with the sub-strate or substrates. The disclosure also includes the method for preparing these composite structures.

Description

~'h~

Background of the Invention Adhesive blends for polar substrates and the resulting composite structures are finding great utility in industry at the present time. It is well known that blends of high density polyethylene (HDPE) or low den-sity polyethylene tLDPE) or ethylene-vinyl acetate copol-ymers (EVA) with a high density polyethylene grafted with suitable unsaturated carboxylic acid or carboxylic acid anhydrides or other acid derivatives are adherent to certain polar polymers such as polyamides. On the other hand, adhesion to certain other polar polymers such as polyesters and saponified ethylene-vinyl ace-tate copolymer (ethylene-vinyl alcohol copolymer [EVO~]) is not sufficiently great in many instances.
The blends of this invention provide high bond strength to polyester and ethylene-vinyl alcohol copolymer. The adhesion compared to that with blends prepared hitherto is very much improved. Also, the excellent bond strength to polyolefins, and other polar substrates, is retained. These polar substrates include polyvinyl alcohol polymers, metalsl polyamides, glass, paper, wood, etc.

Summary of the Inventio~
The invention in its broader aspect pertains to an adhesive blend consisting essentially of (a) about 0.1 to less than about 40 parts by weight in the blend of a graft copolymer of about 70-99.95 wt.% of a polyethylene backbone grafted with about 30-0.05 wt.~ of at least one grafting monomer comprising at least one polymerizable ethylenically unsaturated carboxylic acid or carboxylic acid derivative for a total of 100%, and (b) about 0.1-99 parts by weight in the blend of low density polyethylene or ethylene-unsaturated ester copolymers, or linear low density poly-ethylene or mixtures thereof~ and (c) about 0.1-99 parts by weight in the blend of a blending component comprising a homopolymer or copolymer or mixtures thereof, of an ~-olefin of 4-15 carbon atoms, for a total of components (a), (b) and (c) of 100 parts by weight.
The invention also comprehends composite structures comprising one or more substrates and a blend of the above as the adhesive in contact with the substrate or substrates.
."i -la-More particularly, by grafting suitable unsaturated carboxylic acids or acid derivatives such as aci.d anhydrides, acid chlorides, acid esters, salts, amides and imides and the like to a polyolefin such as polyethylene of den-sity 0.910 to 0.970 g/cc, and blending the resultant polymer (a) with (b) a low density or linear low den-sity polyethylene of density of about 0.910 to 0.945 g/cc or an ethylene-unsaturated ester copolymer resin, and (c) a poly(~-olefin) selected from homopolymers and copolymers of olefin monomers with 4-lS carbon atoms, such as poly(butene-l) [also known as polybutylene], poly(hexene-l), poly(4-methyl pentene-l) and the like, l~ .

we have obtained a~hesive resins with excellent adhe-sive strength both to polyolefins and to various sub-strates.
These substrates include polar polymers such as nylon and other polyamides, ethylene-vinyl alcohol co-polymers, polyvinyl alcohol and its copolymers, polyes-ter po]ymers, polyurethanes and other carbonyl-contain-ing polymers, metals, glass, paper, wood and the like.
The resulting composite structures can be in the form of films, containers, bottles, tubes, sheets, etc. They can be made by any method known to one skilled in the art. Examples of such methods are co-extrusion, molding, lamination, coating ox a combina-tion of these methods or any other method for joining dissimilar materials known to those skilled in the art. The poly(~-olefin) aids in the adhesion to the polar substrate since without its presence, poorer ad-hesion is obtained to polar substrates including polar polymers and especially to ethylene-vinyl alcohol co-polymers and polyesters.

Description of the Preferred Embodiments The term polyethylene used for the graftingbackbone includes ethylene polymers, copolymers and terpolymers of ethylene with one or more alkenes such as propylene, butene-l, hexene-l, 4~methyl pentene-l, octene-l and such other unsaturated aliphatic hydro-carbons. Linear polyethylenes, either high, medium or low density polyethylenes, are preferred.
Also, it is preferable sometimes to graft the blends of two or more of the above homopolymers and copolymers.
The term "low density or linear low density pol-yethylene or an ethylene-unsaturated ester copolymer"
used as a blending component ~b) includes the linear low density polyethylene generally prepared by trans-ition metal ca-talys~s such as compounds of titanium, vanadium, aluminum, chromium and the like, or branched low density polyethylene prepared by -the high pressure process or copolymers of ethylene and unsaturated esters such as vinyl acetate, ethyl acrylate, methyl acrylate, ethyl methacrylate and the like. The range of density can be from about 0.91 to 0.97 g/cc and MI of 0.1 to 100 g/10 min. It is preferable to use a 0.91 to 0.93 g/cc density polyethylene having a melt index of 0.5 to 20 g/10 min.
The term "poly(N-olefin)" used as blending component (c) includes poly(butene-l), poly(hexene-1), poly(octene-1), and other homopolymers and copolymers that contain greater than 50 wt.% of ~-olefins (with 4-15 carbon atoms). It is preferable to use poly(bu-tene-l) of melt index 0.5 to 50 g/10 min. as determined by ASTM Test Procedure D1238 and a density range of 0.88 to 0.93 g/cc for this invention.
The backbone of the graft copolymers includes homopolymers of ethylene and copolymers of ethylene with up to 40 wt.% of such higher olefins as propylene, l-butene and l-hexene and may contain di- or triolefins as are used commercially in ethylene~propylene terpol-ymers such as ethylidene-norbornene, methylenenorborn-ene, 1,4-hexadiene and vinylnorbornene. Also, it is preferable sometimes to graft blends of two or more of the above homopolymers, copolymers and terpolymers.
While the above polymers represent the preferred em-bodiments of our invention, they should not be regarded as limiting in any way.
The unsaturated carboxylic acids or acid anhy-drides used as the grafting monomers include compounds such as acrylic acid, methacrylic acid, fumaric acid, maleic acid, maleic anhydride, 4-methyl cyclohex-4-ene-1,2-dicarboxylic acid anhydride, bicyclo(2.2.2)oct-5-ene-2,3-dicarboxylic acid anhydride, 1,2,3,4,5,8,9,10-octahydronaphthalene-2,3-dicarboxylic acid anhydride,

2-oxa-1,3-di]cetospiro(4.4)non-7-ene, bicyclo(2.2.1~
hept-5-ene-2,3-dicarboxylic acid anhydride, maleopimar-ic acid, tetrahydrophthalic anhydride, x-methylbicyclo (2.2.1)hept-5-ene-2,3~dicarboxylic acid anhydride, x-methylnorborn-5-ene-2,3-dicarboxylic acid anhydride, norborn-5-ene-2,3-dicarboxylic acid anhydride, Nadic anhydride, methyl Nadic anhydride, Himic anhydride, methyl Himic anhydride and other fused ring monomers described in U.S. patents 3,873,643 and 3,882,194, both assigned to the assignee hereof.
Cografting monomers as described in U.S. patent

3,8~2,194 are also useful for preparing the graft co-polymers of this invention.
Included among the conjugated unsatura~ed esters suitable for cografting are dialkyl maleates, dialkyl fumarates, dialkyl itaconates, dialkyl mesa-conates, dialkyl citraconates, alkyl acrylates, alkyl crotonates, al]cyl tiglates and alkyl methacrylates where alkyl represents aliphatic, aryl-aliphatic and cycloaliphatic groups containing 1-12 carbon atoms.
Esters particularly useful in the cografted copolymers of this invention are dibutyl maleate, diethyl fumarate and dimethyl itaconate. Among the acids and acid an-hydrides particularly useful in the cografted copolymers of this invention are maleic anhydride, fumaric acid, x-methylbicyclo(2.2.1)hept-5-en~-2,3-dicarboxylic acid anhydride and bicyclo(2.2.1)hept-5-ene-2,3-dicarboxylic acid anhydride.
It is often desirable to use more than one monomer in either or both classes of monomers in order to control the physical properties of the final prod-ucts. The method in general consists of heating a mixture of the polymer or polymers and the monomer or monomers with or without a solvent. The mixture can be heated to above the melting point of the polyolefin with or without a catalyst. Thus, the grafting occurs in the presence of air, hydroperoxides, other free radical catalysts or preferably in the essential absence of those materials where the mixture is maintained at elevated temperatures and (if no solvent is used) preferably under high shear.
A convenient method of accomplishing the reac-tion is to premix the ingredients and then extrude the composition through a heated extruder. Other mixing means, such as a Brabender mixer, a Banbury mixer, roll mills and the like may also be employed for the process.
In order to prevent undue increase in molecular weight with a possibllity of some cross-linking at elevated temperatures. it is desirable to carry out the reaction in a closed vessel. A conventional single or multiple screw extruder accomplishes this result without the use of auxiliary equipment and for this reason is a particularly desirable reaction vessel.
The graft and cograft copolymers are recovered by any method or system which separates or utilizes the graft copolymer that is produced. Thus, the term in-cludes recovery of the copolymer in the form of pre-cipitated fluff, pellets, powders and the like, as well as further chemically reacted or blended pellets, powders and the like or in the form of shaped articles formed directly from the resulting copolymer.
The resulting copolymers are found to consist of about 70-99.95 wt.% of polyethylene and about 0.05-30 wt.% of the unsaturated acid or acid anhydride or mixtures.
The cograft copolymers consist of about 50-99.9 wt.% of polyolefin, about 0.05-25 wt.% of the unsatur-ated acid or acid anhydride or mixtures thereof and about 0.05-25 wt.% of the unsaturated ester and mix-tures thereof. These resulting graft copolymers arecapable of being blended or reacted with a wide variety ~!r3ao~

of other materials to modify the copolymer further.
Adhesive blends of this invention can be used in composites containing polar substrates such as nylon, ethylene vinyl alcohol copolymers (EVOH), poly--vinyl alcohol (PVA), polyester, polyurethane, metals,etc. These compositions can be just two layers or they can be three or more layers with materials which adhere to either layer being added to the structure. For instance, polyolefins like polyethylene (PE), ethylene vinyl acetate copolymers (EVA) or ethylene copolymers with other monomers and polypropylene ~PP) can ~e used in these layers. It is obvious that many combinations -can be made by one skilled in the art of using the principles disclosed.
The methods for this joining can be lamination, coextrusion, extrusion lamination, coextrusion coating or any other method for joining dissimilar materials to form composite structures known to those skilled in the art.
Some e~amples of these composites are: adhesive of this invention/nylon, adhesive/polyethylene, adhe-sive/polyester, adhesive/ethylene-vinyl acetate copol-ymer, adhesive/ethylene-vinyl alcohol copolymer, adhesive/aluminum, adhesive/steel, adhesive/glass, adhesive/wood, adhesive/leather, polyolefin/adhesive/
nylon, polyolefin/adhesive/EVOH, adhesive/nylon/adhe-sive/polyolefin, polyolefin/adhesive/EVOH/adhesive/
polyolefin, polyolefin/adhesive/polyester, EVA/adhesive/
EVOH, EVA/adhesive/polyesters, polyolefin/adhesive/
polyes-ter/adhesive, and polyolefin/adhesive/polyester/
adhesive/polyolefin.
Examples of other combinations are aluminum/
adhesive/aluminum or adhesive/aluminum/adhesive or polyolcfin/adhesive/aluminum/adhesive/polyolefin.
Other metals such as copper, steel, brass, etc. can also be used. Dissimilar metal examples are:

aluminum/adhesive/copper, aluminum/adhesive/steel, aluminum/adhesive/brass, etc. One could also have combinations in which one has a metal/adhesive/polar polymer. Examples of these would be aluminum/adhesive/
nylon or aluminum/adhesive/EVOH, or steel/adhesive/
nylon/adhesive/steel. Here again, one skilled in the art can find a number of obvious combinations from the principles described above.
The term "polyester" used as a substrate in these composi-tes includes homopolymers (essentially comprising the reaction product of a dicarboxylic acid or its de-rivative with a diol or its derivative) and copolymers (essentially comprising the reaction product of one or more dicarboxylic acids or its derivatives with one or more diols or its derivatives). The dicarboxylic acids and the diols referred to above can be aliphatic, aromatic or alicyclic. Examples of such carboxylic acids are terephthalic acid, isophthalic acid, cyclo-hexane-dicarboxylic acids and the like.
Examples of such diols are ethylene glycol, di-hydroxy-propene (propylene glycol), dihydroxy-butene (butylene glycol), dihydromethylbenzene, dihydromethyl-cyclohexane and the like.
The composites of this invention can be used to manufacture many different useful articles. They can be used as packaging films, blow molded bottles, co-extruded sheet which can be thermoformed into container, coatings on glass bottles or wood or metal or even to join two metals, either the same metal or dissimilar metals, into a lamination.
In preparing the blends in the examples below from the above graft copolymers, ethylene homopolymers and copolymers, and poly(~-olefin)s, any blending equipment or technique may be used. As an example, blends can be prepared in an electrically heated Bra-bender Plasticorder mixing head using a scroll type .

mixer under the following conditions: temperature -325F, rotor speed - 120 rpm and mixing -time - 10 minutes after flux.
All blends preferab7y contain an antioxidant package.
In most of the specific examp]es, the resultant blends were compression molded into fllms approximately 0.005-0.007 inches thick. The films were then heat sealed to the substrate under evaluation at an appro-priate temperature and time.

E mple 1 An electrically heated C.W. Brabender mixingunit was used for blending 45 wt.% of a linear low density polyethylene resin of a melt index of 3.1 g/10 min. and a density of 0.921 g/cc with 45 wt.% of a poly (butene-l) of melt index 1.0 g/10 min. and density 0.910 g/cc and 10 wt.% of a high density polyethylene of density 0.96 g/cc grafted with x-methyl bicyclol2.2.1) hept-5-ene-2,3-dicarboxylic acid anhydride (XMNA) such that the grafted high density polyethylene had a melt index of 1.5 g/10 min. and graft level of 1.5 wt.%.
The blend was tested for adhesion to ethylene-vinyl alcohol copolymer film on a heat sealer set at 430F
for 1 sec. An inseparable bond was obtained, and the adhesion was greater than 6.6 lb/in.
Example 2 The polyl~butene-l) in Example 1 was changed to one with a melt index of 1.8 g/10 min. and a density of 0.915 g/cc. The blend thus prepared gave an insep-arable bond with adhesion greater than 6.9 lb/in when heat sealed to a film of ethylene-vinyl alcohol copoly-mer at ~30F for 1 sec.

'3~34~
g Example 3 The poly(butene-l) in Example 1 was changed to one ~ith a mel-t index of 2.0 g/10 min. and a density of 0.908 g/cc. The blend thus prepared when heat-sealed at 430F and 1 sec. to the following substrates gave results as follows:

Substrate ~dhesion Bond Ethylene-vinyl alcohol copolymer >7.3 lb/in inseparable 10 Medium density poly-ethylene 3 MI, 0.932p >7.5 lb/in inseparable Nylon 6 3.9 lb/in elongation Example 4 An electrically heated C.W. Brabender mixing unit was used for blending 45 wt.% of a medium density polyethylene of melt index 3 g/10 min. and density of 0.932 g/cc with 45 wt.% of a poly(butene-l) of melt index 2.0 g/10 min. and of density of 0.908 g/cc and 10 wt.% o~ high density polyethylene grafted with x-methyl bicyclo(2.2.1)hept-5-ene-2,3-dicarboxylic acid anhydride similar to that used in Example 1. This blend was then heat-sealed to nylon 6 and to ethylene-vinyl alcohol copolymer at 430F and 1 sec. The 25 adhesion to ny:Lon 6 was 2.6 lb/in and 3.0 lb/in to ethylene-vinyl alcohol copolymer.
Example 5 The linear low density resin in Example 3 was replaced by one with a melt index of 2.5 g/10 min. and a density of 0.918 g/cc. The blend thus made was heat-sealed to films of nylon 6 and ethylene-vinyl al-cohol copolymer at 430F and 1 sec. The adhesion was J~

greater than 5.4 and 7.1 lb/in respectively. Insep-arable bonds were obtained.
Examples 6-22 -An electrically heated C. W. Brabender mixing unit was used for blending a linear low density poly-ethylene (LLDPE) resin of melt index 2.0 g/10 min.
and density 0.920 g/cc with a poly(butene-l) of melt index 2.0 g/10 min. and a density of 0.908 g/cc and a high density polyethylene grafted with x-methyl bicyclo(2.2.1)hept-5-ene-2,3-dicarboxylic acid anhy-dride (XMNA) similar to that used in Example 1 such that the following weight percent composition ratios were used for making blends. These blends were then heat-sealed to ethylene-vinyl alcohol copolymer at 430F for 1 sec. The adhesions obtained are listed in the last column below:

_ ~ o~ D O O O 0~ ~ ~ ~ ~ ~ r-O ~ 9 ~ o o ~ ~n In ~ ~
. ~ A A A /\ ~1 ~1 A A
S

OOOOOOOOOOOOOOOOO
S-~ O
U oQ
O

~: In Q) o o o o o In o o o o o n In ~ ~1 O . Q

a n W o o o o o u ) o o o o o ~ D ~ O
a~

O
a O
r~ ~ r~ co a~ o ~ n ~ o ~ r~
x l'hq~041 Examples 23-25 An elec-trically heated C.W. Brabender mixing unit was used for blending a lineax 1QW density poly-ethylene resin (LLDPE) of melt index 1 g/10 min. and a density of 0.924 g/cc with a poly(butene-l) resin (PB) of melt index 2.0 g/10 min. and a density of 0.908 gtcc along with a h~gh density polyethylene grafted with x-methyl bicyclo(2.2.1)hept-5-ene-2,3-dicarboxylic acid anhydride (XMNA) in the following percentage ratios. The adhesions were carried ollt in a heat-sealer at 430F for 1 sec. The adhesion values inlb/in obtained to aluminum film (Al~), ethylene-vinyl alcohol copolymer film (EVOH) and nylon 6 (N-6) are given below:

3~

O
~ :~
J) A A
R
O :~ o~ CO CO ~, ~ In O ~D
~ r~ A A

~r ~ o h o o o m ~ o o O
.

C: O O O
~ ~ a~ I~ H

11:

P~ ~
t`l ~ N
rd Examples 26-27 Instead of the linear low density polyethylene used in Examples 23 and 25, a low density polyethylene resin (LDPE) of melt index 1.8 g/10 min. and a density of 0.922 g/cc was used to make blends #26 and 27 re-spectively. The adhesion values obtained after heat-sealing to EVOH and Nylon 6 are given below:

a) ~D0:~ ~
~' o A

,~
~ ~:
rC 0~
A A

o o ~ U ., a m o o P~
.

P~
o O

~, a) P~
X

3~

Exam~les 28-29 -Instead of the linear low density polyethylene used in Examples 23 and 24, a low density polyethylene (LDPE) of melt index 2.5 g/10 min. and a density of 0.919 g/cc was used in formulating blends #28 and 29 respectively. A linear low density polyethylene grafted with x-methyl bicyclo(2.2.1)hept-5-ene-2~3-dicarboxylic acid anhydride with melt index of 5.1 g/10 min. was used instead of the grafted HDPE. The adhesions ohtained to ethylene-vinyl alcohol copolymer film (EVOH) and to nylon 6 film are given below in lbs/in:

~D ~ O
~ ~ ~ .
r~
~) O A
~n ~
~ æ
o tn *
a) :~ ~ CJ~
~: ~ ~ t-~¢ ~1 A

~_I O O
r-l ~1 ~ Q
m ~

~ m O O
a .
~ O O ~
a~ ~
o tn " ,U
t" ~ .
. a) a~ .
*

. -18-Examples 30-31 The low density polyethylene used in Examples 28 and 29 was substituted by another low density polyeth-ylene of broad molecular weigh~c distrlbution with a melt inde~ of 5.5 g/10 min. and a density of 0.923 g/cc. The graft copolymer used in these cases was that used in Example 1. Adhesions obtained to ethylene-vinyl alcohol copolymer film (EVOH) and to a copoly-ester film are given below in lbs/in:

td ~:
h Q) ,_ U~
,Q ul ~ ~ r~
~ a) . .
U~ ~
$ P~ ~a o ~: ~ .
o .
r~
o . . o LO
r~ A
V
U~
~ ~
t) a a a~ u~
~d ~ In o rl o o ~:
m o ,1 ,~
~ C) h .~ ~ o ~4 o o In a) ~:
. ~
~ a: I o o >1 t) r r~
o o Ul ~
... o~ o ~ ~ ~
~ ~
a) ~I td a, (~i a) u~
U~ ~
td O
1) ~ 0 P o ~1 r~ ~ ~
d ~ a rX r~

Example 32 The blend used in Example 29 was tested for adhesion to the same copolyester tested in Examples 30 and 31. The adhesion obtained was greater than 7.9 lbs/in.
Example 33 The blend used in Example 7 was tested for ad-hesion to a commercial rubber-modified acrylonitrile-methacrylate copolymer film with the heat sealer set at 350F for 1 sec. The adhesion obtained was greater than 8.1 lbs/in.
Example 34 A blend of 80% low density polyethylene used in Example 28, 10% poly~butene-l) copolymer used in Example 3 and 10% of the high density polyethylene graft copolymer used in Example 1 gave an adhesion greater than 410 lbs/in when heat-sealed to a poly-ethyleneterephtha]ate film (PET) with the heat sealer set at 500F and 5 sec.
Example 35 A blend of 80% ethylene-vinyl acetate copolymer with melt index of 12.0 g/10 min. and 12% vinyl acetate content, 10% of the poly(butene-l) used in Example 3 and 10% of the linear low density polyethylene graft copolymer used in Example 28 gave an adhesion greater than 4.6 lb/in when heat-sealed at 350F and 1 sec. to aluminum foil.
Examples 36-37 Blends of an ethylene-vinyl acetate copolymer 30 (EVA) of melt index 3.0 g/10 min. and 9% vinyl acetate content with poly~butene-l) used in Example 3 and 10%
of the linear low density polyethylene graft copolymer used in Example 28 were prepared with the following compositions. These b~ends were tested for adhesion to aluminum (Al) foil with the Sentinel heat sealer set at 250F and 1 sec. The adhesion values obtained are shown below in lbs/in:

U~
~n ~1 ~
o r~
o U~
s ~ ml o o ~ ~1 ~J
m ~ ~ .
o O
d s~

o o ~ ~ ~ :
Pl ~

=~"
a) P

Examples 38-39 Blends 38 and 39 were prepared similar to blends in Examples 36 and 37, respectively, except the ethyl-ene-vinyl acetate copolymer (EVA) was changed to the one used in Example 35. These blends were then tested for adhesion to ethylene-vinyl alcohol copolymer film (EVOH) with the Sentinel heat sealer set at 430F
and 1 sec. The results of the adhesion are shown below in lbs/in:

'~I) .4 U~ ~: a~ ~
o ~ ~ U) , ,o, .

a) . o ~1 Q
~:q O o o h ~ 1 ~ .
P- gl o o ~ .

' ..
co a~
~ ~ ~ .

. . ~

. -24-Examples 40-41.
Blends were prepared with the following compo-sitions containing the linear low density polyethylene used in Example 6, poly(butene-l) used in Example 3, and a high density polyethylene graft copolymer grafted with maleic anhydride. The adhesiolls obtained to ethylene-vinyl alcohol copolymer (EVOH) when heat-sealed at 430F for 1 sec. are shown below:

~3~)~3~L

U~
.4 U~
~ ,~ U~
O O
~>
~1 A
O
., a .

ml o O
~1 ~: h m r~
o rl ~
O O O
t~` ~ ~J r-l a) h a P. ~
o o ~:~ a~ ~o . ~

,Q)~ ., P o ,~
X

_xamples 42-43 Blends were prepared with the following composi-tions containing the linear low density polyethylene used in Example 6, the high density graft copolymer used in Example 1, and poly(4-methyl pentene-l) (P4MP).
These blends were tested for adhesion to aluminum foil, nylon 6 film, and ethylene-vinyl alcohol copolymer (EVOH) film with the heat sealer set at 430F and 1 sec., respectively. The adhesions shown below are in lbs/in:

~ '.S ~ ~ o fd ~
S~ ~ ~ :
U~
Q
U~
O ~ I O o ~r J~
O ~ ~ .
,~ . a~
Q) O
U~ .

I O o .~. -~r ~ ~

~ S~
~ '~i ,~ Op aJ O o o o t~ ~
a~
U h S~ ~
O
P~ ~
o o In ~:~ a~

1~
a O

, ., . -28-Examples 44-45 -The blends used in Examples 31 and 29 were cast--coextruded with ethyl-vinyl alcohol copolymer (EVOH~. The coextruded cast films obtained had a tot.al thickness of about 3 mils. The adhesive layer of this invention had a thickness of 1.5 mil. The adhesior,s obtained were greater than 1.8 lb/in with blend No. 3:L
and 2.0 lb/in with blend No. ~9. The film elongated during the T-peel test in each case.

Glossary of T~rms Al - aluminum foil EVA - ethylene vinyl acetate copolymer EVOH - ethylene-vinyl alcohol copolymer HDPE - high density polyethyl.ene LDPE - low density polyethylene N-6 - Nylon-6 film LLDPE - linear low density polyethylene PE - polyethylene PB - poly(butene-l) PETG - polyethylene terephthalate glycol-modifled PP - polypropylene PVA - polyvinyl alcohol P4MP - poly(4-methyl pentene-1) PET - polyethylene terephthalate 5 XMNA - x-methylbicyclo(2.2.1)hept-5-ene- 2,3-dicarboxylic acid anhydride Having described our invention as related to the embodiments set out therein, it is our intention that the invention be not limited by any of the de-tails of description, unless otherwise specifi.ed, butrather be construed broadly within its spirit and scope as set out in the appended claims.

Claims (71)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:
1. An adhesive blend consisting essentially of:
(a) about 0.1 to less than about 40 parts by weight in said blend of a graft copolymer of about 70-99.95 wt.%
of a polyethylene backbone grafted with about 30-0.05 wt.%
of at least one grafting monomer comprising at least one polymerizable ethylenically unsaturated carboxylic acid or carboxylic acid derivative for a total of 100%, and (b) about 0.1-99 parts by weight in said blend of LDPE, or ethylene-unsaturated ester copolymers, or LLDPE
or mixtures thereof, and (c) about 0.1-99 parts by weight in said blend of a blending component comprising a homopolymer or copolymer or mixtures thereof, of an .alpha.-olefin of 4-15 carbon atoms, for a total of components (a), (b) and (c) of 100 parts by weight.
2. The blend of claim 1 wherein said ethylene-unsaturated ester copolymers of (b) comprise a copolymer of ethylene and vinyl acetate or ethyl methacrylate or ethyl acrylate or methyl acrylate or methyl methacrylate.
3. The blend of Claim 1 wherein said LLDPE of (b) comprises a copolymer of ethylene and an unsaturated hydrocarbon.
4. The blend of Claim 3 wherein said hydrocarbon comprises propylene, butene-1, 4-methyl pentene-1, hexene-1 or octene-1.
5. The blend of Claim 1 wherein said .alpha.-olefin of component (c) comprises butene-1, 4-methyl pentene-1, hexene-1, octene-1 or pentene-1, or mixtures thereof.
6. The blend of claim 1 wherein said grafting monomer comprises at least one of acrylic acid, metha-crylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, maleic anhydride, 4-methyl cyclohex-4-ene-1,2-dicarboxylic acid anhydride, bicyclo(2.2.2)oct-5-ene-2,3-dicarboxylic acid anhydride, 1,2,3,4,5,8,9,10-octahydronaphthalene-2,3-dicarboxylic acid anhydride, 2-oxa-1,3-diketospiro(4.4)non-7-ene, bicyclo(2.2.1)hept-5-ene-2,3-dicarboxylic acid anhy-dride, maleopimaric acid, tetrahydrophthalic anhydride, norborn-5-ene-2,3-dicarboxylic acid anhydride, Nadic anhydride, methyl Nadic anhydride, Himic anhydride, methyl Himic anhydride, and x-methyl bicyclo(2.2.1) hept-5-ene-2,3-dicarboxylic acid anhydride.
7. A composite structure comprising:
(a) a substrate, and adhered thereto (b) a blend according to claim 1.
8. The composite structure of claim 7 wherein said substrate comprises polyolefins, polar polymers, solid metals, glass, paper, wood, leather or cello-phane.
9. The composite structure of claim 7 wherein said substrate comprises nylon.
10. The composite structure of claim 7 wherein said substrate comprises aluminum.
11. The composite structure of claim 7 wherein said blend is according to claim 2.
12. The composite structure of claim 7 wherein said blend is according to claim 3.
13. The composite structure of claim 7 wherein said blend is according to claim 4.
14. The composite structure of claim 7 wherein said blend is according to claim 5.
15. The composite structure of claim 7 wherein said blend is according to claim 6.
16. The composite structure of claim 7 wherein said substrate comprises ethylene-vinyl alcohol copoly-mer.
17. The composite structure of claim 7 wherein said substrate comprises polyesters.
18. The composite structure of claim 7 wherein said substrate comprises ethylene homopolymers and co-polymers.
19. The composite structure of claim 7 wherein said substrate comprises a rubber-modified acryloni-trile-methacrylate copolymer.
20. A composite structure comprising:

(a) two or more substrates with adjacent pairs adhered together by (b) an intervening layer of a blend according to claim 1.
21. The composite structure of claim 20 where-in said (a) comprises a polar substrate and nylon.
22. The composite structure of claim 20 wherein said (a) comprises a polar substrate and ethylene-vinyl alcohol copolymer.
23. The composite structure of claim 20 wherein said (a) comprises a polar substrate and aluminum.
24. The composite structure of claim 20 wherein said (a) comprises a polar substrate and a polyester or a copolyester.
25. The composite structure of claim 20 wherein said (a) comprises polar substrates.
26. The composite structure of claim 20 wherein said (a) comprises ethylene homopolymers and copolymers and a polar substrate.
27. The composite structure of claim 20 wherein said blend is according to claim 2.
28. The composite structure of claim 20 wherein said blend is according to claim 3.
29. The composite structure of claim 20 wherein said blend is according to claim 4.
30. The composite structure of claim 20 wherein said blend is according to claim 5.
31. The composite structure of claim 20 wherein said blend is according to claim 6.
32. The composite structure of claim 20 wherein said structure comprises PP/adhesive/nylon in which the adhesive is said blend of claim 1.
33. The composite structure of claim 20 wherein said structure comprises PE/adhesive/nylon in which the adhesive is said blend of claim 1.
34. The composite structure of claim 20 wherein said structure comprises EVA/adhesive/nylon in which the adhesive is said blend of claim 1.
35. The composite structure of claim 20 wherein said structure comprises polyolefins/adhesive/vinyl alcohol polymers in which the adhesive is said blend of claim 1.
36. The composite structure of claim 20 wherein said structure comprises EVA/adhesive/EVOH in which the adhesive is said blend of claim 1.
37. The composite structure of claim 20 wherein said structure comprises PE/adhesive/polyester in which the adhesive is said blend of claim 1.
38. The composite structure of claim 20 wherein said structure comprises PE/adhesive/aluminum in which the adhesive is said blend of claim 1.
39. The composite structure of claim 20 wherein said structure comprises EVA/adhesive/aluminum in which the adhesive is said blend of claim 1.
40. The composite structure of claim 20 wherein said structure comprises PE/adhesive/steel in which the adhesive is said blend of claim 1.
41. The composite structure of claim 20 wherein said structure comprises PE/adhesive/copper in which the adhesive is said blend of claim 1.
42. The composite structure of claim 20 wherein said structure comprises EVA/adhesive/glass in which the adhesive is said blend of claim 1.
43. The composite structure of claim 20 wherein said structure comprises PE/adhesive/wood in which the adhesive is said blend of claim 1.
44. The composite structure of claim 20 wherein said structure comprises PE/adhesive/polyurethane in which the adhesive is said blend of claim 1.
45. The composite structure of claim 20 wherein said structure comprises PP/adhesive/polyester in which the adhesive is said blend of claim 1.
46. The composite structure of claim 20 wherein said structure comprises PP/adhesive/nylon/adhesive/EVA
in which the adhesive is said blend of claim 1.
47. The composite structure of claim 20 wherein said structure comprises PE/adhesive/EVOH/adhesive/PE
in which the adhesive is said blend of claim 1.
48. The composite structure of claim 20 wherein said structure comprises PE/adhesive/nylon/adhesive/
EVA in which the adhesive is said blend of claim 1.
49. The composite structure of claim 20 wherein said structure comprises PE/adhesive/aluminum/adhesive/
EVA in which the adhesive is said blend of claim 1.
50. The composite structure of claim 20 wherein said structure comprises PE/adhesive/EVOH in which the adhesive is said blend of claim 1.
51. The composite structure of claim 20 wherein said structure comprises PP/adhesive/EVOH in which the adhesive is said blend of claim 1.
52. The method of making the composite struc-ture of claim 7 wherein said components are adhered together by methods including blown film coextrusion, east film coextrusion, blow molding coextrusion, lamin-ation, extrusion or coextrusion coating, powder coating, rotomolding, profile coextrusion or wire coating extru-sion or coextrusion.
53. The method of making the composite struc-ture of claim 20 wherein said components are adhered together by methods including blown film coextrusion, cast film coextrusion, blow molding coextrusion, lam-ination, extrusion or coextrusion coating, powder coating, rotomolding, profile coextrusion or wire coating extrusion or coextrusion.
54. The blend of Claim 1 wherein said backbone of (a) comprises polyethylene of a density within the range of 0.910-0.970 g/cc.
55. The blend of Claim 1 wherein said (b) comprises LDPE or LLDPE of a density, within the range of 0.910-0.945 g/cc.
56. The blend of Claim 1 wherein said backbone of (a) comprises ethylene polymers or copolymers of ethylene with one or more alkenes.
57. The blend of Claim 56 wherein said backbone of (a) comprises a linear polyethylene of high, medium or low density.
58. The blend of Claim 56 wherein said backbone of (a) comprises blends of two or more of said polymers or copolymers.
59. The blend of Claim 1 wherein said poly-.alpha.-olefin of blending component (c) comprises poly(butene-1) of melt index 0.5 to 50 g/10 min. and a density within the range of 0.88-0.93 g/cc.
60. The composite structure of Claim 7 wherein the blend is according to Claim 54.
61. The composite structure of Claim 7 wherein the blend is according to Claim 55.
62. The composite structure of Claim 7 wherein the blend is according to Claim 56.
63. The composite structure of Claim 7 wherein the blend is according to Claim 57.
64. The composite structure of Claim 7 wherein the blend is according to Claim 58.
65. The composite structure of Claim 7 wherein the blend is according to Claim 59.
66. The composite structure of Claim 20 wherein said blend is according to Claim 54.
67. The composite structure of Claim 20 wherein said blend is according to Claim 55.
68. The composite structure of Claim 20 wherein said blend is according to Claim 56.
69. The composite structure of Claim 20 wherein said blend is according to Claim 57.
70. The composite structure of Claim 20 wherein said blend is according to Claim 58.
71. The composite structure of Claim 20 wherein said blend is according to Claim 59.
CA000415153A 1982-01-18 1982-11-09 Adhesive blends and composite structures Expired CA1200041A (en)

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DE3301445A1 (en) 1983-12-22
GB2113696A (en) 1983-08-10
DE3301445C2 (en) 1990-06-21
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BE897624A1 (en)
JPS58127772A (en) 1983-07-29

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