CN100532443C - Composition comprising ethylene copolymers and polyolefin - Google Patents

Abstract

Disclosed are compositions of ethylene/(meth)acrylate copolymers, polyolefins (e.g., polyethylene and polypropylene), optional tackifier resins and optional fillers that provide very strong, tight hermetic heat seals yet are easily peelable. These compositions are useful as an adhesive layer in multilayer structures that are useful as packaging lidding films. Also disclosed are packages that comprise these multilayer structures.

Description

Comprise ethylene copolymer and polyolefinic composition

The present invention relates to comprise polyolefine (as polyethylene and polypropylene) and ethylene copolymer composition, comprise as described in composition multilayered structure and comprise as described in the wrapping material of multilayered structure.

Background of invention

Packaging industry adopts film and the container package food and the non-food product product by various thermoplastic resins and preparation of compositions of broad variety.Abounding with product in these are packaged as provides enough protections (as preventing physical disturbance, prevention air or moisture etc.) to prepare to use this product up to the human consumer.The same material of wishing to design a package makes the human consumer wait when appropriate and uses this product easily.Usually, wrapping material are by forming from the rigid container of metal (particularly aluminium), paper, fiberboard or plastics (as polypropylene, crystallization polyethylene terephthalate (CPET) and high-impact polystyrene (HIPS)) preparation and the epiphragma of this container of sealing.Wish sealing between container and the epiphragma provide strong gas-tight seal with protection product and sealing can be easily, neatly by human consumer's strip off.

Conventional composition as the sealing of lid agent comprises the composition that comprises polypropylene, polyethylene, ethylene-vinyl acetate copolymer (EVA), ethene/(methyl) acrylate copolymer or amorphous polyester.They also can contain weighting agent or additive to obtain easily to shell feature.Manyly comprise polyolefinic composition because its excellent machinability, low cost and currently in packaging application, be used as peelable heat-sealing thing for the abundant bounding force of many application.Yet these compositions are not all enough durable to all application.For example many packings wish to keep at low temperatures sealing intensity through refrigeration or freezing to help protection product wherein.Equally, polyolefin compositions (as contain EVA those) thus limited their processing characteristicies at high temperature that limited of thermotolerance.

Therefore, wish that research and development provide than the current composition that improves performance that provides of commercially available sealing agent.

Summary of the invention

The invention provides composition, described composition comprises following component or mainly is made up of following component or is prepared by following component: (a) at least a ethylene copolymer of about 80% weight of about 10-; (b) at least a polyolefine of about 60% weight of about 5-; (c) at least a tackifying resin of about 35% weight of 0-; (d) weighting agent of about 35% weight of 0-.Described ethylene copolymer is meant two or more combination of ethene/(methyl) acrylate copolymer, ethylene/alkyl acrylate copolymer, ethene/(methyl) acrylic copolymer, ethylene/alkyl acrylic copolymer, its ionomer or its.

The present invention also provides multilayered structure, described multilayered structure comprises or by one deck above-mentioned composition and one deck extra play preparation at least at least, described extra play comprises paper tinsel, paper, polyester, polymeric amide, polyolefine, polythene-ethenol, polyethylene vinyl acetate ester, ethylene copolymer or its ionomer, polyvinyl chloride, poly(vinylidene fluoride) or anhydride modified polyolefine.

The present invention also provides and comprises or by the wrapping material of above-mentioned composition and multilayered structure preparation.

The present invention also provides wrapping material, and described wrapping material comprise: (1) comprises and contains one deck paper tinsel at least, cardboard, glass, high density polyethylene(HDPE) (HDPE), polypropylene (PP), high-impact polystyrene (HIPS), polystyrene foamed (EPS), acrylic homopolymer or acrylic copolymer, polycarbonate, polysulfones, amorphous polyethylene terephthalate (APET), crystallization polyethylene terephthalate (CPET), polyvinyl chloride (PVC), voltalef (PCTFE), polyacrylonitrile homopolymer or multipolymer, the container of the structure of polyacetal or Copolyacetal; (2) comprise the peelable lid of above-mentioned multilayered structure.

Detailed Description Of The Invention

Term " (methyl) vinylformic acid " is meant methacrylic acid and/or vinylformic acid.Equally, term " (methyl) acrylate " is meant methacrylic ester and/or acrylate.

Thermoplastic compounds can the mobile polymer materials when being heated under pressure.Melting index (MI) is that polymkeric substance passes through specific mass velocity capillaceous under temperature and pressure control condition.Ji Lu melting index adopts 2160 gram weight to measure according to ASTM 1238 down at 190 ℃ herein, and the MI value record is for restraining/10 minutes.Described thermoplastic compounds is fit to by extruding processing and preparing film and multilayered structure.

That term " paper tinsel " is meant is thin, fexible film or metal (as aluminium) sheet.It also refers to multilayered structure, and wherein layer of aluminum is bonded on other other material layer at least, and condition is that at least one skin of described multilayered structure is aluminium lamination.

Peelable heat seal thing can be designed to have three kinds of different failure modes usually when strip off sealer and sealer or sealer and differential substrate.When with various peel angle and speed under stress each other during strip off, destroy can be the interface, layering or agglutinating.Interfacial seal can be designed to the heat-sealing interfacial failure (being that sealant layer is peeled off from stratum basale neatly) at selected sealing face.In most of the cases, sealing intensity was determined by temperature, pressure and the residence time.The sealer that can not totally peel off can be by the fragment pollution package contents of sealer or lid.Require interface peelable seal thing can prevent this pollution.The layering heat-sealing is designed to destroy at the internal interface of multilayer film structure.This design, destroy interface is arranged in the selected layer in somewhere, membrane structure actual hot sealing layer back.Thickness and will determine the intensity of sealer in the stripping process with the bounding force of selected sublayer boundary.In this case, whole sealant layer is transferred to substrate when membrane structure is stripped from.Deliberately adhesive seal is destroyed and is destroyed in actual sealant layer body.When peel seal under stress and speed, split and the part sealant material transferred to the sealing agent substrate in the inside of sealing ply own.The internal intensity of sealant material is the determinative of heat-sealing thing actual strength.

Described composition can comprise following component or mainly be made up of following component: (a) at least a ethene of about 80% weight of about 10-/(methyl) alkyl acrylate copolymer; (b) at least a polyolefine of about 60% weight of about 5-; (c) at least a tackifying resin of about 35% weight of about 0.5-; (d) weighting agent of about 35% weight of 0-.

Described composition also can comprise following component or mainly be made up of following component or prepared by following component: (a) at least a ethene of about 80% weight of about 40-/(methyl) alkyl acrylate copolymer; (b) at least a polyolefine of about 60% weight of about 20-.Described composition also can mainly be made up of following component: (a) at least a ethene of about 80% weight of about 10-/(methyl) alkyl acrylate copolymer; (b) at least a polyolefine of about 60% weight of about 20-; (c) at least a tackifying resin of about 20% weight of about 10-or (a) at least a ethene of about 60% weight of about 40-/(methyl) alkyl acrylate copolymer; (b) at least a polyolefine of about 40% weight of about 20-; (c) at least a tackifying resin of about 20% weight of about 10-; (d) weighting agent of about 20% weight of about 5-.

Term " ethylene copolymer " is meant the thermoplastic copolymer of derived from ethylene monomer and at least a alkyl acrylate or the copolymerization of alkyl methacrylate comonomer, and wherein said alkyl contains 1-8 carbon atom.Ethene/(methyl) alkyl acrylate copolymer and ethene/(methyl) acrylate copolymer is used interchangeably in this article.For example alkyl acrylate comprises methyl acrylate, ethyl propenoate and butyl acrylate." ethylene/methyl acrylate (EMA) " is meant the multipolymer of ethene (E) and methyl acrylate (MA)." ethylene/ethyl acrylate (EEA) " is meant the multipolymer of ethene (E) and ethyl propenoate (EA)." ethylene/butyl acrylate (being abbreviated as EBA) " is meant the multipolymer of ethene (E) and butyl acrylate (BA).

The amount that adds the alkyl acrylate comonomer of ethene/(methyl) acrylate copolymer can extensively change in principle, from about 1% weight of multipolymer gross weight to height to 40% weight or even higher.The selection of alkyl can be methyl to having or not branched 8 carbon atom alkyls.For example, the alkyl that is used for preparing (methyl) alkyl acrylate comonomer of ethylene copolymer can be 1-4 carbon atom, and (methyl) alkyl acrylate comonomer concentration can be the 5-30 or the 9-27% weight of total ethene/(methyl) acrylate copolymer.Methyl acrylate (tool polar alkyl acrylate comonomer) can be used for preparing the ethylene/methyl acrylate dipolymer.The monomeric concentration of described methyl acrylate copoly can be about 5-30,9-25 or the 9-24% weight of ethylene copolymer.

The alternative single multipolymer of the mixture of two or more ethylene copolymers is as the component (a) in the described composition.When being used for blend, two kinds of ethylene/alkyl acrylate copolymers of suitably selecting can obtain useful especially performance.Such as but not limited to, composition comprises that wherein said ethylene/alkyl acrylate component comprises those of two kinds of differing ethylene/methyl acrylate copolymers.The single EMA grade in two kinds of suitably selected EMA grade mixture replacing blends of available same amount equally for example, the methyl acrylate weight percent content of wherein said mixture and melting index are identical with the institute single EMA grade of alternate.Compare with the composition that only contains single EMA resin grades,, can realize the change of composition properties by in conjunction with two kinds of suitably selected different EMA multipolymer grades.

Described ethene/(methyl) alkyl acrylate copolymer can also be chosen wantonly and comprise at least a other comonomer (comprising (methyl) vinylformic acid, maleic anhydride, glycidyl methacrylate and carbon monoxide) to form terpolymer, for example ethylene/acrylic acid isobutyl ester/methacrylic acid, ethylene/methyl acrylate/maleic anhydride, ethylene/butyl acrylate/glycidyl methacrylate (EBAGMA) and ethylene/butyl acrylate/carbon monoxide (EBACO).

Ethene/(methyl) acrylate copolymer can adopt autoclave or tubular reactor to be prepared according to well-known method in the polymer arts.Copolymerization can be carried out according to continuation method in autoclave.For example, ethene, (methyl) alkyl acrylate (as methyl acrylate) and optional solvents (as methyl alcohol) (referring to as United States Patent (USP) 5,028,674) and initiator add stirred vessel continuously (as United States Patent (USP) 2, the autoclave of disclosed type in 897,183) in.Adding speed can be depending on the concentration of methacrylate monomer in the composition that obtains the target multipolymer required polymerization temperature, pressure and the reaction mixture.In some cases, may wish to adopt telogen such as propane to control molecular weight.Product mixtures can be removed continuously from container.After product mixtures left reaction vessel, multipolymer can separate by ordinary method with solvent (if using) with unreacted monomer, for example evaporated not polymeric material and solvent under decompression and elevated temperature.The autoclave acrylate copolymer can derive from Voridian (commodity are called EMAC), ExxonMobil (commodity are called Optema) and Atofina (commodity are called Lotryl).

As recognized in the art, ethene/(methyl) acrylate that the ethene of tubular reactor produced/(methyl) acrylate copolymer can prepare with more conventional autoclave makes a distinction.Therefore term or phrase " tubular reactor produced " ethene/(methyl) acrylate copolymer are illustrated under high pressure and the elevated temperature ethylene copolymer of preparation in tubular reactor etc., and therein ethylene and (methyl) alkyl acrylate (as methyl acrylate) comonomer dynamic (dynamical) intrinsic result of differential responses separately weaken or partial offset along tubular reactor internal reaction flow process introducing monomer by having a mind to.Confessed as this area, with compare than the multipolymer that in high pressure agitated autoclave reactor, prepares with same comonomer, this tubular reactor copolymerization technique makes along the multipolymer of the relative irregularity of main polymer chain bigger (comonomer more becomes piece to distribute), is tending towards reducing the long-chain side chain, the higher multipolymer of preparation fusing point.

The ethene of the tubular reactor produced of this character/(methyl) acrylate copolymer can commercially availablely derive from E.I.du Pont de Nemours and Company (DuPont), Wilmington, Delaware.

Tubular reactor ethylene/(methyl) acrylate copolymer preparation in high pressure tubular reactors under elevated temperature can comprise along pipeline introduces the reactant comonomer in addition, is not only to prepare in stirring high temperature and high pressure autoclave-type reactor.Similarly ethene/(methyl) acrylate copolymer material can prepare in a series of autoclave reactors, wherein the comonomer displacement is introduced the realization of reactant comonomer (as United States Patent (USP) 3 by multi-region, 350,372,3,756,996 and 5,532,066 is disclosed), can think that equally these materials with high melting point are equivalent to the multipolymer of the tubular reactor produced of the object of the invention.These products can derive from Voridian, commodity EMAC+ by name or EBAC+.

In order further to contrast the multipolymer of conventional autoclave preparation, ethylene/alkyl acrylate copolymer to described tubular reactor produced is illustrated and characterizes, below commercially available ethylene/methyl acrylate copolymer list and relevant fusing point data show: owing to distribute along the very different MA of polymer chain, the EMA resin of tubular reactor produced has much higher fusing point than autoclave EMA:

The multipolymer of autoclave preparation

ExxonMobil, N.J.; Mp=76 ℃ of EMA (21.5% weight MA)

ExxonMobil, N.J.; Mp=69 ℃ of EMA (24% weight MA)

Atofina, France; Mp=80 ℃ of EMA (20% weight MA)

Atofina, France; Mp=73 ℃ of EMA (24% weight MA)

The multipolymer of tubular reactor produced

Mp=88 ℃ of DuPont EMA (25% weight MA)

Mp=95 ℃ of DuPont EMA (20% weight MA)

About the other discussion of the difference of tubular reactor produced and ethylene/alkyl acrylate copolymer autoclave preparation " High Flexibility EMA made from High Pressure TubularProcess (by the high tenacity EMA of high pressure tubular method preparation) " referring to Richard T.Chou, Mimi Y.Keating and Lester J.Hughes, Annual TechnicalConference-Society of Plastics Engineers (2002), 60th (Vol.2), 1832-1836.CODEN:ACPED4 ISSN:0272-5223; AN 2002:572809CAPLUS.

Be applicable to that ethylene/alkyl acrylate copolymer of the present invention can derive from DuPont.The specific examples of ethylene/alkyl acrylate copolymer that derives from DuPont is referring to Table A.

Table A

Ethylene/alkyl acrylate copolymer	Alkyl acrylate % weight	Melt flow (restraining/10 minutes)
			EMA-1	25	0.4
EMA-2	25	0.6
			EMA-3	9	2
EMA-4	14	2
			EMA-5	18	2
EMA-6	24	2
			EMA-7	9	6
EMA-8	20	8
			EMA-9	13	9
EEA-1	12	1
			EEA-2	16	1
EEA-3	15	6
			EEA-4	15	7
EBA-1	7	1.1
			EBA-2	7	1.1
EBA-3	17	1.5
			EBA-4	17	1.8
EBA-5	27	4
			EBA-6	17	7

Described available ethene/(methyl) acrylate copolymer can be different on molecular weight, with melting index (MI) expression, are high extremely about 10 mark on the numeral, list in the Table A.Will with the concrete selection of the polymeric constituent MI grade influence that may be subjected to preparing the multilayered structure method therefor.Preferably MI is about 100 grams/10 minutes of about 0.1-or about 0.5-about 50 or/10 minutes ethylene copolymer of about 30 grams of about 0.50-.

Polyolefine can comprise the homopolymer and the multipolymer of the alkene of 2-8 carbon atom.Polyolefinic example comprises Natene, homopolymer polypropylene, comprise the multipolymer of ethene and comprise the multipolymer of propylene.Polyethylene (PE) can prepare by several different methods, such as but not limited to well-known Ziegler-Natta catalyst polymerization (referring to as United States Patent (USP) 4,076,698 and 3,645,992), metallocene catalyst polymerisation is (referring to as United States Patent (USP) 5,198,401 and 5,405,922) Polymerization catalyst and radical polymerization.Polymerization can be carried out according to solution phase method, gas phase process etc.Polyethylene can comprise linear polyethylene such as high density polyethylene(HDPE) (HDPE), linear low density of polyethylene (LLDPE), extremely low or ultra-low density polyethylene (VLDPE or ULDPE) and branched polyethylene such as new LDPE (film grade) (LDPE).Be applicable to that PE density of the present invention is the about 0.970g/cc of about 0.865g/cc-.Noticeable polyethylene is the multipolymer of ethene and 1-butylene.Containing 12.6% weight 1-butylene, melting index and be 3.5 this multipolymer is to derive from ExxonMobil's

3035.Noticeable another polyethylene is the multipolymer of ethene and 1-octene.Containing 12% weight octene, melting index and be 3.5 this multipolymer is to derive from DuPont Dow Elastomers's

8450.

Polypropylene (PP) polymkeric substance comprises the terpolymer of homopolymer, random copolymers, segmented copolymer and propylene.The multipolymer of propylene comprises the multipolymer of propylene and other alkene (as ethene, 1-butylene, 2-butylene and various pentene isomers etc.), the multipolymer of preferred propylene and ethene.The terpolymer of propylene comprises the multipolymer of propylene and ethene and a kind of other alkene.Random copolymers (being known as statistical copolymer equally) for propylene wherein and comonomer on whole polymer chain with corresponding to the polymkeric substance of propylene with the ratio random distribution of comonomer feed ratio.The segment that segmented copolymer is made up of alfon and form as the segment that the random copolymers of propylene and ethene is formed.Term " polypropylene " is meant arbitrarily or all above-mentioned polymkeric substance that comprise propylene.

Homopolymer and random copolymers can be according to any currently known methods preparations.For example polyacrylic polymer can be based on organometallic compound with contain in the presence of the solid ziegler-natta catalyst systems of titanous chloride and prepare.Segmented copolymer can similarly prepare, and different is propylene is generally at fs self-polymerization at first, in the presence of the polymkeric substance that propylene and other comonomer such as ethene obtain in the fs subsequently in the subordinate phase polymerization.Each stage is can be for example continuous or discontinuously carry out in same reactor or independent reactor in the suspension of the suspension of hydrocarbon diluent, propylene liquid or gas phase.44 and 4.7 chapters of " BlockCopolymers (segmented copolymer) " can be specifically edited referring to D.C.Allport and W.H.Janes about the out of Memory of segmented copolymer and preparation thereof, Applied Science PublishersLtd (1973).

Polyolefine also can carry out modification by one or more polar monomers of introducing a small amount of (generally being lower than about 3% weight), and described polar monomer comprises such as but not limited to vinyl acetate, alkyl acrylate, carbon monoxide, glycidyl methacrylate, (methyl) vinylformic acid and maleic anhydride.The introducing of these polar comonomers can be finished by copolymerization or grafting.

Can use two or more polyolefinic blends.For example LLDPE can with LDPE or HDPE blend so that polyethylene blend or PP and poly-(1-butylene) blend (PB) to be provided.

Described composition can be chosen wantonly and contain tackifying resin.Can use any tackifier (being also referred to as tackiness agent) that those skilled in the art will know that, as US 3,484, those disclosed in 405.This tackifier comprise multiple natural and synthetic resins and rosin material.Described resin can be liquid, semi-solid to solid or solid, comprises the compound amorphous material that is generally the organic compound form of mixtures that does not have sharp melting point and do not have crystallization trend.This resin may be water insoluble, can or can be synthetic resins from plant or animal.Described resin can be the binding property that described composition provides essence and improvement.Suitable tackifier include but not limited to coumarone-indene resin (para-coumarone-indene resin), terpine resin, butadiene styrene resin, polybutadiene, hydrocarbon resin, rosin and wherein two or more combination.

The molecular weight of general coumarone-indene resin is about 500-about 5,000.The example of the commercially available this resin that gets comprises those materials as " Picco "-25 and " Picco "-100 sale.

Terpine resin comprises the vinylbenzene terpenes, and molecular weight can be about 600-6,000.The example of commercial resins is as " Piccolyte " S-100, " Staybelite Ester " #10 (EastmanChemical, Kingsport, Tennessee) (it is the glyceryl ester of staybelite) and " Wingtack " 95 (it is a polyterpene resin) sell.Noticeable terpine resin base tackifier are derived from many limonene (a kind of monomer that reclaims from citrus industry), with

C115 derives from Pinova.

The molecular weight of butadiene styrene resin can be about 500-about 5,000.The commercially available prod example is sold as " Buton " 100, and molecular weight is liquid butadiene-styrene copolymer resin of about 2,500.

The molecular weight of polybutadiene can be about 500-about 5,000.Commercial examples is that the molecular weight sold as " Buton " 150 is about 2, the liquid polybutadiene resin of 000-about 2,500.

Hydrocarbon resin can make by the catalyzed polymerization of the selected cut that obtains in oil refining, and molecular weight can be about 500-about 5,000.The example of this resin is those of conduct " Piccopale "-100, the sale of " Amoco " and " Velsicol " resin.Similarly, can comprise the polybutene that obtains from isobutene polymerisation as tackifier.

Tackifier also can comprise rosin material, lower molecular weight (as 1300) vinylbenzene hardened resin (as the material of selling as " Piccolastic " A-75), disproportionation pentaerythritol ester and this class aromatics of conduct " Velsicol " WX-1232 sale and the multipolymer of aliphatic monomers system.Can be used for rosin of the present invention and can be natural gum, timber or starex, but preferred starex.Same described rosin material can be modified rosin, as dimerization colophonium, staybelite, nilox resin or rosin ester.Ester can be by making with the polyvalent alcohol esterification rosin that contains 2-6 alcohol radical.

Noticeable another tackifying resin is the RegaliteR1125 (a kind of hydrocarbon) that derives from Eastman Chemical.

The inventory more comprehensively of tackifier can be referring to TAPPI CA Report #55, in February, 1975,13-20 page or leaf (Technical Association of the Pulp and Paper Industry, Atlanta, GA. publication), the document is listed more than 200 kinds of commercially available tackifier resins.

Described tackifier can directly combine with ethylene copolymer or disclosed other component or pre-fusion compound for the masterbatch preparation.This technology is at US6,255,395 and JP 2,002 173,653 in describe.For example many limonene can be copolymer blended with preparation tackifier masterbatch with ethene/octane, and described tackifier masterbatch can join the composition remaining ingredient in follow-up blend operation.

But two or more independent tackifier of blend.

Composition of the present invention also can be chosen wantonly and contain weighting agent.The adding of weighting agent can improve temperature tolerance and influence the peel seal characteristic of composition.

Weighting agent can comprise inorganic compound particle, as mineral and salt.The weight of the weighting agent that comprises in the described composition is the function of described weighting agent density.Weighting agent granularity and shape also may influence the performance of blend.The weighting agent of fine size generally is tending towards producing higher blend viscosity, and they are also more expensive.No.9 Whiting (about 95% by 325 orders) represents the feasible mid point of roughness, availability and cost aspect.Preferred weighting agent is that lime carbonate and talcum (are mainly Mg ₃Si ₄O ₁₀(OH) ₃), talcum most preferably.Filling dose in the present composition can be about 30% weight of about 0.001-.

Before in being blended into the present composition, weighting agent can the pre-blend in masterbatch with ethylene/alkyl acrylate or polyolefine.For example talcum can be copolymer blended with preparation weighting agent masterbatch with ethylene/methyl acrylate (20% weight MA), and described weighting agent masterbatch can join the composition remaining ingredient in follow-up blend operation.

Weighting agent also can be and ethene/(methyl) alkyl acrylate of component (a) and the incomplete compatible polymers material of polyolefinic combination of component (b), for example polystyrene resin is meant the homopolymer of vinylbenzene or alpha-methyl styrene or the multipolymer of vinylbenzene and unsaturated monomer (such as but not limited to ethene, butylene, divinyl or isoprene).Specific examples includes but not limited to the random or segmented copolymer of ethylene/styrene, ethene/divinyl is random or segmented copolymer and hydrogenation and partially hydrogenated butadiene/styrene copolymers.Same useful is the polystyrene that further modification improves impact property, is commonly referred to high-impact polystyrene or HIPS.Can use the blend and the mixture of polystyrene type.Specific examples includes but not limited to derive from the HIPS of NovaChemicals or the ethylene/styrene multipolymer that Dow Chemical sells.

Can there be other additive, as component, static inhibitor and the antifogging agent of oxidation inhibitor and thermo-stabilizer, ultraviolet (UV) photostabilizer, tinting material, pigment and dyestuff, weighting agent, matting agent, slipproofing agent, softening agent, anti, compatilizer, improvement surface characteristic such as frictional coefficient (COF), other processing aid etc.The amount of these additives is generally 0.001-20 or 0.01-15% weight in the described composition, and condition is the binding property (weight percent of these additives is not included in the total weight percent of the composition that defines in the summary of the invention) that they do not reduce described composition.Generally, many this additives can be 0.01-5% weight.It should be noted that oxidation inhibitor can be 0.01-1% weight.Oxidation inhibitor derives from Ciba Geigy Inc., Tarrytown, New York with trade(brand)name Irganox.For example phenolic antioxidant such as Irganox E201 (CAS No.10191-41-0) or derivatives thereof can add in the composition.Irganox 1010 (CAS No.6683-19-8) is for being applicable to another oxidation inhibitor of the present invention.It should be noted that equally the additive that improves surface characteristic such as frictional coefficient, antiblocking or the cooling roller demoulding can be 0.001-5% weight.For example, this additive is the dispersion of silicon-dioxide (2% weight) in ethylene/methacrylic acid, as the carrier enriched material be blended into resin (as

20B derives from DuPont).

The described composition of optional adding of this additive can carry out according to any currently known methods, for example mixes, extrudes each component mixture, conventional masterbatch technology etc. by dried.

Adhesive resin composition of the present invention can be by ethene/(methyl) acrylate copolymer component (a), polyolefine (b), optional tackifier (c) and optional weighting agent (d) preparation of adopting mixing tank (as Henschel mixing tank, V-type mixing tank, ribbon mixer or tumbler mixer) mix predetermined quantities; or after mixing; with described mixtures of fusion kneading such as single screw extrusion machine, twin screw extruder, milling machine, banbury mixers, granulation subsequently, melt extrude, granulate or pulverize described mixture.

After suitably melt blending or heating mixed, described composition can be extruded by die head through coextrusion.The thickness of the sealing agent of extruding is preferably about 1-400 micron, more preferably 5-100 micron, also more preferably 10-30 micron.

Perhaps, the present composition can be extruded and be the about 1-100 micron of thickness, more preferably 5-100 micron, and the more preferably film of 10-75 micron also is laminated to paper, paper tinsel or subsequently as the film of multilayered structure part.

Adhesive resin composition of the present invention can be used for making various substrates or polymkeric substance bonding mutually.Generally, described goods are by heat-sealing bonding or bonding.

Final binder composition can be directly used in as fusion coextrusion, or it can rope form or granularly extrude or be decreased to small pieces or powdery is used for suitable applicator.But its casting or extrude and be film or netted for using subsequently.In this shaping form, it can be placed on treats between the adhesive substance, subsequently by heat and pressure activated.Described tackiness agent can apply by any normally used hot melt applicator.

Although these compositions can the professional think that favourable any thickness applies, preferably adopt the layer thickness of 0.0002mils-10mils (0.0000005-0.025 centimetre).

The present invention also provides sealer or the laminating material that is applicable to container, wrapping material, film etc. by heat-sealing, and described sealer or laminating material have good heat sealability and can peel off easily.

Film and coating can be from described preparation of compositions and lamination or coating to other film or structures.Perhaps, described composition can be simultaneously coextrusion with other material.Generally speaking, adhesive resin composition disclosed herein can use by various forms, as adhesive sheet, adhesive tape or laminating material product because it is chemical and physicals can be used as binding agent and tackiness agent is peeled off and sealed binder to provide so-called.

Described composition can be used for providing heat-sealing for the sealing of the polyvinyl chloride that needs the peelable seal thing (PVC), polyvinylidene dichloride (PVDC), PP, polyethylene terephthalate (PET) and polystyrene equally.Described composition can provide wide sealing intensity scope and existing wideer, the higher temperature action pane of heat sealable system of ratio.

It is general solvent-based system based on EVA or amorphous PET that sealant systems is selected in existing confession, is applied to carrier web by roller or gravure system.These coatings are generally extremely thin, are limited to the component that is dissolved in solvent system.The present invention is not subjected to the restriction of sealant layer thickness or combination of components to obtain required heat-seal strength or stripping performance.Sealing agent disclosed herein can not contain solvent, solves about using the environmental problem of solvent.Solvent-free sealing system can be simpler and has greater flexibility, and this can improve the economy of final sealing agent net preparation.

The present invention also comprises improved heat-sealable material, for the container by PCTFE fluoropolymer preparation provides the peelable gas-tight seal of sealing intensity wide ranges (derived from the many homopolymer of trifluorochloroethylene polymeric and multipolymer with trade(brand)name

The commercially available Honeywell that derives from, Inc., Morristown, New Jersey).PCTFE can provide high damp proof and antioxygen property, makes wrapped product have the longer storage life.The PCTFE fluoropolymer has the barrier propterty suitable with paper tinsel.If composition does not have good bounding force with fluoropolymers such as PCTFE, the use of PCTFE may be restricted.

The PCTFE layer can be directly bonded to the structure that forms the preparation container on the PVC second layer.Because described PVC has high avidity to many heat-sealable materials, thereby as sealing face.So since it than PCTFE more cheap it also provide main body for described structure.Two kinds of materials all have high-clarity and formability.PVC is not enough as sealing face possibility oxygen and moisture barrier propterty.When top layer exclusion seal agent net was heat sealed on the PVC, the barrier propterty of PCTFE can not realize fully.Oxygen and moisture penetration cause the storage life to shorten by the PVC between heat-sealing cover material and the PCTFE.

PCTFE can become the innermost layer and the sealing substrate of described heat-sealing top net, makes final packaging realize that whole barrier properties of PCTFE cause the storage life longer.Equally, by with PCTFE as internal layer rather than skin, PCTFE attenuation as much can not appear among the preparation method.The easy unlatching transparent container of the peelable lid of high-barrier to provide the storage life to improve can be provided for this.

Sealant material disclosed herein can be used for pharmaceutical industry and is used for Blister Package and non-medicine, and described packing is user-friendly to patient and other packing user.It can provide tempting and cheap packing for being based upon the medicine of being convenient to scale operation and the sale of other products in some sense.Described packing can be held one to a plurality of goods, as food, capsule form medicine, tablet, medical appliance, syringe, lozenge, pill etc. or non-thing medicine, as other commodity of anti-block of poisonous substance, catalyzer, cleaning composition, battery and needs and moisture.

The film that comprises the present composition can adopt any method preparation well known by persons skilled in the art in fact.Film can be the single or multiple lift polymeric film.Equally, described film and membrane structure generally can carry out casting, extrude, coextrusion, lamination etc., comprises and adopt the whole bag of tricks (as blown film, mechanical stretching etc.) orientation (single shaft or twin shaft).

The invention still further relates to the coextrusion or laminar structure of single or multiple lift, described structure comprise described herein tackiness agent as one deck (generally being hot sealing layer) so that the bonding between other packing composition to be provided.The peel seal intensity of these compositions makes and various lid substrate bondings comprises that ethylene vinyl acetate, polyethylene, polystyrene, polypropylene, polyethylene terephthalate, polyvinyl chloride, metal (as aluminium), spunbond polyolefine are (as the commercially available DuPont of deriving from

Oriented polyester (as The substrate of preparation such as (DuPont)), described peel seal intensity can be regulated by the amount and the kind of ethene/(methyl) acrylate copolymer, polyolefine inclusion, tackifier and/or weighting agent in the change binder composition.

The present invention also provides multilayered structure, and described multilayered structure comprises at least one layer by preparation of compositions disclosed herein and comprises the other layer of paper tinsel, paper, polyester, polymeric amide, polyolefine, polythene-ethenol, polyethylene vinyl acetate ester, ethene/(methyl) acrylic copolymer and ionomer, polyvinyl chloride, polyvinylidene dichloride and anhydride modified polyolefin with at least one.Noticeable multilayered structure comprises the noticeable as defined above composition of one deck at least.Preferred structure comprises at least one deck preferred composition as defined above.

Described multilayer polymer sheets can comprise at least three class layers, include but not limited to outermost structural or abuse layer (abuse layer), interior barrier layer, packing layer (bulking layer) and/or binder layer and innermost layer, described innermost layer contacts with the package contents of expection and is compatible with it, can form essential sealing (for example most preferably heat-sealing) to itself and the other parts of packing.Also can exist other layer with help these layers to be bonded together as tackiness agent or " bonding " layer.

Described outermost structural or abuse layer can be oriented polyester or orientation or non-oriented polypropylene, but also can comprise orientation or non-oriented polymeric amide (nylon) or polyethylene (as HDPE) or paper or paper tinsel.When optical clear, but this layer is preferably reversal printing and influence that do not prepared the seal temperature of packing employing, and this is because the whole thickness of the multilayered structure of packing obtains sealing.When external structure or abuse layer optics were opaque, this layer can be through surface printing, and was optional subsequently with protective coating or lacquering.The thickness of this layer can be controlled the rigidity of film, can be about 100 μ m of about 10-or the about 50 μ m of about 12 μ m-.

Described internal layer can comprise one or more layers barrier layer, and this depends on the atmospheric condition (oxygen, humidity, light etc.) of product in the energy potential impact packing.Barrier layer can be for example metal-coated PP or PET, polythene-ethenol (EVOH), polyvinyl alcohol, polyvinylidene dichloride, polyolefine, aluminium foil, nylon, its blend or matrix material and related copolymers thereof.Barrier layer thickness can be depending on factors such as product susceptibility and required storage life.

Described internal layer can comprise one or more layers packing layer.Generally form structure with finished predetermined depth by adopting cheaply general polymer to add this layer.Packing layer can be for example blend of polyolefine, polyolefine polar copolymer, polyester and/or various packing layer components.Packing layer also is fit to add reface thing and the fragment that generates in the preparation process.The fragment that generates from the material that should not sell for a certain reason or cut the material that the limit generates from the work in-process volume and can grind and be attached to the filling that internal layer provides relatively low cost for example.

Internal layer can comprise one or more layers binder layer.This binder layer generally is used for described outer structure layer is bonded to described internal layer, and described internal layer is bonded to described innermost layer, or when internal layer during only as tackiness agent, directly bonding is outer to innermost layer.

Described innermost layer can be sealant layer, its available above-mentioned composition preparation.

Described structure and barrier layer can be in conjunction with comprising several polymer layers, and described polymer layer effectively intercepts moisture and oxygen and has and is suitable for processing and/or the main body mechanical property (for example transparency, toughness and penetration resistance) of wrapped product.In some applications, the function of structure and barrier layer can be incorporated in the appropriate resin simple layer.For example nylon or PET are suitable for structure and barriers function.

Polymeric amide comprises aliphatic polyamide, amorphous polyamides or its mixture.Aliphatic polyamide can refer to the blend or the mixture of aliphatic polyamide, aliphatic copolyamide and these polymeric amide, for example polyamide 6, polyamide 6 .66 and blend and mixture.Polyamide 6 .66 is with trade(brand)name

C4 " and

C35 " commercially availablely derive from BASF or with trade(brand)name

The commercially available Ube Industries Ltd that derives from.Polyamide 6 can trade(brand)name The commercially available Honeywell International that derives from.

Described film also comprises other polymeric amide, as United States Patent (USP) 5,408, and those disclosed in 000,4,174,358,3,393,210,2,512,606,2,312,966 and 2,241,322.

Described film can also comprise the partially aromatic polymeric amide, and for example amorphous nylon resin 6-I/6-T is (with trade(brand)name

PA is commercially available to derive from DuPont or with trade(brand)name

The G 21 commercially available EMS-Chemie AG that derive from).

Ionomer is the multipolymer of alkene (as ethene), unsaturated carboxylic acid (as acrylic or methacrylic acid) and optional softening comonomer, wherein at least a or multiple basic metal, transition metal or alkaline earth metal cation (as sodium, potassium or zinc) are used for a part of acidic group of neutralized copolymer, obtain performance enhanced thermoplastic resin.For example " ethene/(methyl) vinylformic acid (E/ (M) AA) " is meant the multipolymer of ethene (E)/vinylformic acid (AA) and/or ethylene/methacrylic acid (MAA), and described multipolymer is formed ionomer by one or more basic metal, transition metal or alkaline earth metal cation to the small part neutralization.Terpolymer also can be from alkene (as ethene), unsaturated carboxylic acid and other comonomer (as (methyl) alkyl acrylate) preparation to provide " softer " resin that can be neutralized to form than soft ionomer.Ionomer is known to usually, and their preparation method for example has been disclosed among the US 3,344,014.

But acid anhydrides or the ethene improved and alfon of acid and multipolymer can be used as extrusioning adhesive layer (being also referred to as " bonding " layer) with the bonding of improving polymer layer (when described polymkeric substance bonding to each other when bad), thereby improve the multilayered structure middle level with layer bonding.The composition of tack coat can be depending on needs agglutinating adjoining course composition in the multilayered structure.Polymer arts technician can select suitable tack coat according to other material that is used for structure.Various binding layer compositions are with trade(brand)name

The commercially available DuPont that derives from.

Can use EVOH with about 50% molar ethylene of about 20-.Suitable polythene-ethenol multipolymer is with trade(brand)name

Commercially availablely derive from Kuraray or with trade(brand)name

The commercially available Nippon Goshei that derives from.

Being adapted at this PVDC polymkeric substance and multipolymer with making coatings or film can be for example with trade(brand)name

The commercially available Dow Chemical that derives from.

Being used for film of the present invention from the above-mentioned composition preparation can carry out according to any currently known methods.For example may adopt so-called " blown film " or " flat die " method by the nascent film of extrusion compositions preparation.Can make the tubular film stent that obtains make blown film by polymer composition being extruded by annular die and with airflow.Can prepare the flat film of casting by composition being extruded by flat die.The film that leaves die head contains the roller (cooling roller) of fluid circulating or obtains plastic casting film by the water-bath cooling by at least one.Film can carry out cutting with routine techniques (as cutting) and obtain packaging film.

Behind instant quenching of film or casting, described film can further be orientated.This method comprises extrudes laminar flow molten polymer, quenching extrudate and the step of the described quenching extrudate of orientation at least one or a plurality of direction." quenching " described and fully is cooled to below its fusing point to obtain the extrudate of solid film material.

That described film can be is non-oriented, in single shaft direction orientation (as vertically) or in biaxially oriented orientation (as vertical and horizontal).Described film can stretch by two mutually perpendicular directions in described thin film planar and carry out diaxial orientation to reach the satisfactory combination of mechanics and physicals.

The orientation and the stretcher of single shaft or biaxially oriented film are well known in the art, and those skilled in the art can make it adapt to preparation film of the present invention.Referring to for example United States Patent (USP) 3,278,663,3,337,665,3,456,044,4,590,106,4,760,116,4,769,421,4,797,235 and 4,886,634.

Blown film can adopt two bubble extrusion methods to be orientated, wherein diaxial orientation can be realized by following steps simultaneously: extrude nascent pipe (primary tube), described nascent pipe is with after quenching, heat and cause horizontal orientation with the air pressure inside stent subsequently again, with differential speed press from both sides or given pace under the transfer roller stretching cause machine-direction oriented.

The method that obtains the orientation blow mollding film is well known in the art as two bubble technology and can carries out described in 044 according to United States Patent (USP) 3,456.Melt extrude in the nascent Guan Kecong annular die.This is extruded nascent pipe and can cool off fast at utmost to reduce crystallization.It can be heated to its orientation temperature (as by water-bath) subsequently.At the unitary oriented region of film preparation, by inflation preparation second pipe, thereby film makes under the temperature that produces expand (simultaneously preferred) on the both direction at the transverse radial stent, and at longitudinal stretching; Reducing suddenly fast of drawing point thickness followed in the expansion of tubing.Tubular film planishes by nip rolls subsequently again.Film can expand again and by annealing steps (thermofixation), be heated once more to adjust shrinkage at film described in this step.

Described film can prepare by extrusion method, and described method causes the polymer chain in the film generally extruding the direction arrangement.Line polymer has quite high intensity in differently-oriented directivity after the height uniaxial orientation, but transverse strength is lower.This arrangement can increase film in the intensity of extruding on the direction.

Described film can pass through or other standard method in corona discharge, ozone or the industry is handled.

Multilayered structure can be depending on the thickness of ethylene copolymer-polyolefin hot-seal layer to the sealing intensity of container.Hot sealing layer thickness can be about 10-40 μ m or about 10-30 μ m.

Multilayered structure can be used as wrapping material and is used for various packaging application.They also can be used as industrial film, as shelter film, and wherein film is pressed onto substrate (as paper tinsel or polyester or acrylic acid or the like) through thermosphere, and is peelable when no longer needing surface protection.

Described wrapping material also can be through further processing, such as but not limited to printing, embossing and/or paintedly provide the wrapping material of product information and/or joyful packaging external appearance to be provided as the human consumer.

Some example of multilayer film structure of the present invention is listed below, wherein said sealant layer can be from above-mentioned ethylene copolymer-polyolefin compositions preparation, wherein " adh " is meant aforesaid adhesive composition, " tie " but be meant extrusioning adhesive or tack coat, and " Ink " is meant aforesaid printing.

Multilayer film structure comprise have shown in the blown film of structure:

Polymeric amide (nylon)/tie/EVOH/tie/ sealing agent; Or

The PP/tie/EVOH/tie/ sealing agent.

Multilayer film structure comprise have shown in the adhesive lamination film of structure:

Ink/ paper tinsel/adh/PE/PE/ sealing agent; Or

The PET/Ink/adh/PE/tie/EVOH/tie/ sealing agent.

Multilayer film structure comprise have shown in the extruding-coating film of structure:

Ink/ paper tinsel/tie/ sealing agent;

The PET/PVDC/Ink/tie/ sealing agent;

The Ink/PET/tie/ sealing agent;

Ink/ paper/PE/ sealing agent.

Multilayer film structure comprise have shown in the extruding-laminated film of structure:

The PET/PVDC/Ink/tie/ sealing agent;

The PET/adh/ sealing agent; Or

PET/adh/ nylon/tie/ sealing agent.

Above-mentioned multilayered structure can add in the packing (as adding lid container) by standard method known in this area.Multilayered structure can be used as the cover material of container.Packing or container comprise molding, compacting or the thermoformed container that contains said structure and/or multilayered structure.Except above-mentioned materials, rigid container can contain other material, for example with various additive agent modified to obtain to be suitable for to prepare the fluoropolymer resin of the polymer-modified blend of container, as toughness CPET.Also available other additive of material is as going nested dose of (denesting agent) modification, and also useful additives such as weighting agent carry out modification.Container can be and contains innermost layer product contact layer, can be and intercept or the internal layer of packing layer and the laminated vessel of skin or abuse layer.

This container can be used for packing for example yogourt, pudding, custard, gelatin, fruity sauces products such as (for example apple sauce).They also can be used for packing soft cheese and water juice.The packing of Miao Shuing can be used as meat and packing freezing or the refrigeration meals herein.Packing of the present invention can comprise that also dried food for example is used for the noodles of water reconstruction and the packing of seasonings.They also can be used for packing dried snacks for example cooky, potato chips etc.

Following embodiment only is used to illustrate, and limits the scope of the invention and should not be construed as.

Embodiment

With the standard blending technology from following material preparation composition so that the composition as the embodiment 1-20 that sums up the following table 1 to 3 to be provided.Adopt and prepare the comparative example like the following material type.

Material therefor:

EMA-7: ethene/(methyl) acrylate (9% weight) multipolymer, MI is 6, derives from DuPont.

EMA-8: ethene/(methyl) acrylate (20% weight) multipolymer, MI is 8, derives from DuPont.

EMA-9: ethene/(methyl) acrylate (13% weight) multipolymer, M is 9, derives from DuPont.

PE-1: the multipolymer of ethene and 1-butylene, MI be 3.5 (as

3035 derive from ExxonMobil).

PE-2: the multipolymer of ethene and 1-octene (12% weight octane), MI be 3.5 (as

8450 derive from DuPont Dow Elastomers).

Add-1: silicon-dioxide 2% a weight fraction prose style free from parallelism of ethylene/methacrylic acid (as

20S2 derives from DuPont).

Tack-1: derived from the tackifier resins of many limonene, as

C115 derives from Pinova.

Tack-2: tackifier resins derives from Eastman as Regalite R1125.

The blend of the EMA-8 of the talcum of Filler-1:50% weight and 50% weight.

Antiox-1: oxidation inhibitor

1010.

EVA-1: ethylene/vinyl acetate (7% weight) multipolymer, MI is 7, derives from DuPont.

EVA-2: ethylene/vinyl acetate (17% weight) multipolymer, MI is 30, derives from DuPont.

EVA-3: ethylene/vinyl acetate (12% weight) multipolymer, MI is 8, derives from DuPont.

EVA-4: ethylene/vinyl acetate (25% weight) multipolymer, MI is 25, derives from DuPont.

EVA-5: ethylene/vinyl acetate (17% weight) multipolymer, MI is 30, derives from DuPont.

Ionomer-1: with zinc part neutral ethylene/methacrylic acid, MI is 14, derives from DuPont.

Among the table 1-3, listed amount is a weight part, and "--" means that component does not exist in described composition.

Table 1

Embodiment	The EMA multipolymer	PE-1	Tack-1	Add-1	Antiox-1
						1	EMA-7 52.95	30	15	2	0.05
2	EMA-7 62.95	20	15	2	0.05
						3	EMA-7 42.95	40	15	2	0.05
4	EMA-9 52.95	30	15	2	0.05
						5	EMA-9 67.95	30	--	2	0.05
6	EMA-7 67.95	30	--	2	0.05
						7	EMA-9 82.95	--	15	2	0.05

Table 2

Embodiment	The EMA multipolymer	PE-2	Tack-1	Add-1	Filler-1	Antiox-1
							8	EMA-7 50.95	27.5	15	1.5	5	0.05
9	EMA-7 45.45	23	15	1.5	15	0.05
							10	EMA-7 42.95	20.5	15	1.5	20	0.05
11	EMA-7 40.45	18	15	1.5	25	0.05
							C12	EMA-9 78.50	--	--	1.5	20	--
C13	EMA-9 73.50	--	--	1.5	25	--
							C14	EMA-9 68.50	--	--	1.5	30	--
C15	EMA-9 64.50	--	--	1.5	35	--
							16	EMA-7 52.95	30	15	2	--	0.05
30	EMA-7 52.95	26.25	18.75	2	--	0.05
							31	EMA-7 35.45	143	15.2	--	35	0.05

Table 3

Embodiment	The EMA multipolymer	PE-1	Tack-1	Add-1	Filler-1	Antiox-1
							C17	EMA-9 85	--	--	--	15	--
C18	EMA-9 88	--	--	2	10	--
							C19	EMA-9 83	--	--	2	15	--
20	EMA-9 47.95	25	15	2	10	0.05

Table 4 general introduction some heat salable composition as known in the art.They generally can be described as the composition that comprises following component: (a) at least a ethylene/vinyl acetate copolymer of 20-90 weight part; (b) at least a polyolefine of 10-50 weight part; (c) at least a tackifying resin of 1-40 weight part; (d) the about 50 weight part weighting agents of 0-.

Table 4

Comparative example C1	% weight	Comparative example C2	% weight
				EVA-1	40	EVA-1	40
PE-1	40	PE-2	40
				Tack-2	20	Tack-2	20
Comparative example C3	% weight	Comparative example C4	% weight
				EVA-1	52	EVA-1	52
PE-1	35	PE-2	35
				Tack-1	10	Tack-1	10
EVA-2	3	EVA-2	3
				Comparative example C5		Comparative example C6
EVA-1	49.95	EVA-1	49.95
				PE-1	30	PE-2	30
Tack-1	15	Tack-1	15
				EVA-2	5	EVA-2	5
Antiox-1	0.05	Antiox-1	0.05
				Comparative example C7		Comparative example C8
EVA-3	54.95	EVA-3	54.95
				PE-1	30	PE-2	30
Tack-1	15	Tack-1	15
				Antiox-1	0.05	Antiox-1	0.05

Table 5 general introduction is some physicals of described heat salable composition herein.Table 5 shows that the physicals of composition is very similar to the physicals of known heat salable composition.

Table 5

Composition	Melting index	Fusing point	Vicat softening point
				Comparative example C1	8	94	68
Comparative example C2	8	97	67.7
				Comparative example C3	6.9	95	72
Comparative example C4	6.0	95.5	70.7
				Comparative example C5	8.6	93	66
Comparative example C6	9.7	94	67.5
				Comparative example C7	8.6	93	66
Comparative example C8	10.3	91	65.9
				Embodiment 1	7.1	93	64
Embodiment 16	7.3	97	65.9

The test of adopting among the embodiment

Melting index (MI) is according to ASTM D-1238, and condition E adopts 2160 gram weight to measure down at 190 ℃, and the MI value is with gram expression in/10 minutes.Density is measured according to ASTM D-792.Fusing point (m.p.) adopts differential scanning calorimetry (DSC) to measure according to ASTM D-3418.Vicat softening point is measured according to ASTM D-1525.

Stripping strength: sealing ply adopts standard seal equipment and condition to be sealed in the substrate so that one inch wide seal strip to be provided.Except as otherwise noted, layer separates and the velocity of separation that at room temperature is configured to 12 inch per minute clocks with " the T-type is peeled off " stretches on stretching testing machine at sealing ply/substrate interface.The required mean force of separating layer is stripping strength (a gram/inch) divided by width record.Generally, three to five times the separation determination value is averaged together, is recorded in the table.

The failure mode that is recorded among the table 6-10 characterizes with following descriptor:

" P "-totally peel off from substrate

" FT "-film is torn (tearing up)

" FB "-film breaks

" CL "-coating rises

" ZP "-zip mode is peeled off

" T "-viscosity

" NT "-inviscid

" D "-layering

What table 6 provided the single thin film that comprises embodiment 6 compositions peels off data (gram/inch, room temperature, 50% relative humidity, three multiple are average), described single thin film shown in the temperature lower seal to several substrates, having with the Sentinel sealer is the one inch wide sealing that prepared in 1 second with 40psi, the residence time.

Table 6

Embodiment 21

Employing standard lamination prepares multilayer cover material of the present invention, described multilayer cover material comprise the thick paper tinsel skin of 2.0mil, 0.5mil thick have 12% weight methacrylic acid and MI be 13.5 ethylene acid copolymer (as

1214 derive from DuPont) middle layer and the thick embodiment 1 composition inner sealant layer of 1.0mil.Table 7 provide shown in the temperature lower seal peel off data (gram/inch, five multiple mean values) to the multilayer cover material of several suprabasil embodiment 21.Described sealing adopts the Sentinel sealer to prepare so that one inch sealed width to be provided for 1 second in 40psi, the residence time.

Table 7

The comparative example 22

Employing standard lamination prepares the multilayer cover material, and described multilayer cover material comprises the thick amorphous polyester of 1.0mil (deriving from DuPont Teijin Films as Mylar LBT) skin, the thick high-density polyethylene layer of 1.0mil, the thick high density polyethylene(HDPE) of 0.5mil and low density polyethylene blends layer and the thick comparative example C6 of 0.5mil composition inner sealant layer.Table 8 provide shown in the temperature lower seal to suprabasil this multilayer cover material peel off data (gram/inch, five multiple mean values) with embodiment 21 relatively.Sealing adopts the Sentinel sealer to prepare so that one inch sealed width to be provided for 1 second in 40psi, the residence time.

Table 8

Table 7 and 8 data comparison shows that: composition of the present invention provides, still strippable sealing stronger than known encapsulant when as sealant layer, shows that when remaining on freezing temperature sealing intensity still less reduces.

Embodiment 23 and comparative example 24-26

Preparation comprises the film of embodiment 4 compositions and is heat sealed on the film that comprises PCTFE.Sealing adopts the Sentinel sealer to prepare so that one inch sealed width to be provided for 1 second in 40psi, the residence time.

Table 9 provides that embodiment's 23 under room temperature and 50% relative humidity peel off data (25 multiple mean value).Comparative example in the table 9 is the cover material based on solvent-based coating.Comparative example C24 is the solvent-based coating of styrene-based-divinyl, and comparative example C25 is the solvent-based coating based on amorphous polyester.Two kinds of materials all derive from the HueckFolien of Germany.

Table 9

Data in the table 9 show: comparative example C24 provides the low strength peelable seals.Comparative example C25 provides the sealing of sufficient intensity, shows that product may packaged material contamination but layering takes place.Embodiment 23 provides intensity good sealing, follows clean all the time peel seal.

Comparative example 27 and embodiment 28

Prepare film and be heat sealed on the film that comprises PCTFE according to the description among the embodiment 23.Described PCTFE film adopts Medipak Model CP-2I wrapping machine (115 ℃ of upper and lower forming temperatures) to be thermoformed into the bubble wrap base in advance.With 2, the sealing load of 500psi and 25cpm (container per minute) are heat sealed on the PCTFE face of formed film the embodiment film under differing temps.

Table 10 provides peels off data (5 multiple mean value) under room temperature and 50% relative humidity.Comparative example C27 uses the film that comprises the blend that is used for comparative example C26 (table 9).Adopt comparatively high temps C26 fully to be sealed on the PCTFE although table 10 shows, in blow-by under these low seal temperatures to the PCTFE film.Embodiment 28 films seal and totally peel off from the PCTFE film, even adopt low seal temperature.

Table 10

¹The Nominal Width of bubble wrap heat-sealing.

Embodiment 32-36

Adopt to do the blend of blend standard blending technology list in table 11 and 12 material then melting mixing prepare composition.The melt blended material of PE-2 that adopts the Tack-1 of 80% weight and 20% weight is as the source of (with the PE-2 that replenishes) of the Tack-1 in these compositions (amount of those components of record is for adding the total amount behind the pre-composition in the table 11 and 12).

Table 11

Embodiment	The EMA multipolymer	PE-2	Tack-1	PE-3	Filler-1	Antiox-1
							32	EMA-7 24.95	13	12	25	25	0.05
33	EMA-7 14.95	18	12	25	30	0.05
							34	EMA-7 14.95	13	12	30	30	0.05

Table 12

Embodiment	The EMA multipolymer	PE-2	Tack-1	PE-3	Filler-2	Antiox-1
							35	EMA-7 34.95	18	12	25	10	0.05
36	EMA-7 34.95	13	12	25	15	0.05

Claims (23)

1. composition, described composition mainly is made up of following: (a) at least a ethene of 10-80% weight/(methyl) alkyl acrylate copolymer; (b) at least a polyolefine of 5-60% weight; (c) at least a tackifying resin of 0.5-35% weight; (d) weighting agent of 5-20% weight, wherein the alkyl in (methyl) alkyl acrylate has 1-4 carbon atom, and described ethene/(methyl) alkyl acrylate copolymer comprises the repeating unit derived from (methyl) alkyl acrylate of 5-30% weight.

2. the composition of claim 1, the amount of wherein said at least a ethene/(methyl) alkyl acrylate copolymer is a 40-80% weight.

3. the composition of claim 1, wherein said at least a polyolefinic amount is a 20-60% weight.

4. the composition of claim 1, wherein said at least a polyolefinic amount is a 20-40% weight.

5. the composition of claim 1, the amount of wherein said at least a tackifying resin is a 10-20% weight.

6. the composition of claim 1, wherein said (methyl) alkyl acrylate is a methyl acrylate, described ethene/(methyl) alkyl acrylate copolymer comprises the repeating unit derived from the methyl acrylate of 9-24% weight.

7. the composition of claim 1, the melting index of wherein said ethene/(methyl) alkyl acrylate copolymer are 0.1-100 gram/10 minutes, and described ethene/(methyl) alkyl acrylate copolymer comprises two kinds of differing ethylene/methyl acrylate copolymers.

The composition of 8 claims 1, the melting index of wherein said ethene/(methyl) alkyl acrylate copolymer are 0.5-50 gram/10 minutes, and described ethene/(methyl) alkyl acrylate copolymer comprises two kinds of differing ethylene/methyl acrylate copolymers.

9. the composition of claim 1, wherein said weighting agent is inorganic mineral or salt.

10. the composition of claim 1, wherein said weighting agent is and described ethene/(methyl) alkyl acrylate, polyolefin component or both incomplete compatible polymers materials.

11. the composition of claim 1, wherein said weighting agent are polystyrene.

12. the composition of claim 1, wherein said ethene/(methyl) alkyl acrylate copolymer comprise derived from two or more the repeating unit of combination of maleic anhydride, glycidyl methacrylate, carbon monoxide or its.

13. the composition of claim 1, wherein said polyolefine is Natene, homopolymer polypropylene, comprise the multipolymer of ethene, comprise two or more combination of the multipolymer of propylene or its, and described multipolymer comprises two or more combination of 1-butylene, 1-hexene, 1-octene or its.

14. the composition of claim 1, wherein said tackifying resin are two or more combination of coumarone-indene resin, hydrocarbon resin, rosin material or its, and derived from many limonene.

15. the composition of claim 1, wherein said tackifying resin are two or more combination of terpine resin, butadiene styrene resin or its, and derived from many limonene.

16. the composition of claim 1, wherein said ethene/(methyl) alkyl acrylate copolymer prepares in tubular reactor.

17. multilayered structure, described multilayered structure comprise at least one comprise composition or by preparation of compositions the layer, at least one second layer and optional at least one the 3rd layer of existing, wherein said composition are among the claim 1-16 described in each: the described second layer comprises following or by following preparation: paper tinsel, paper, polyester, polymeric amide, polyolefine, polythene-ethenol, the polyethylene vinyl acetate ester, the ionomer of ethene/(methyl) acrylic copolymer and ethene/(methyl) acrylic copolymer, polyvinyl chloride, polyvinylidene dichloride or maleic anhydride modified polyolefine; Described the 3rd layer comprises following or by following preparation: paper tinsel, cardboard, glass, high density polyethylene(HDPE), polypropylene, polystyrene, acrylic homopolymer, acrylic copolymer, polycarbonate, polysulfones, amorphous polyethylene terephthalate, crystallization polyethylene terephthalate, PVC, voltalef, polyacrylonitrile homopolymer, polyacrylonitrile multipolymer, polyacetal or Copolyacetal.

18. the multilayered structure of claim 17, wherein said the 3rd layer comprises following or by following preparation: high-impact polystyrene or polystyrene foamed.

19. the multilayered structure of claim 17, described multilayer also comprise the 3rd layer or by the 3rd layer of preparation.

The multilayered structure of 20 claims 17 is as the purposes of the cover material of packing or container.

21. pack or container for one kind, described packing or container comprise composition or multilayered structure or by composition or multilayered structure preparation, wherein said composition is among the claim 1-16 described in each, and described multilayered structure is among the claim 17-19 described in each.

22. the packing of claim 21 or container, the wherein said second layer comprises the voltalef fluoropolymer.

23. the packing of claim 21 or 22 or container, described packing or container are bubble wrap, bag, molding, compacting or thermoformed container.