CN1239973A - Dispersible film - Google Patents
Dispersible film Download PDFInfo
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- CN1239973A CN1239973A CN97180326A CN97180326A CN1239973A CN 1239973 A CN1239973 A CN 1239973A CN 97180326 A CN97180326 A CN 97180326A CN 97180326 A CN97180326 A CN 97180326A CN 1239973 A CN1239973 A CN 1239973A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/016—Additives defined by their aspect ratio
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
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Abstract
Compounding ingredients for unvulcanized rubber, or bales of unvulcanized rubber are packaged in filler reinforced film or bags made from an ethylene alpha -olefin copolymer having a Vicat softening point below 90 DEG C and a melting point below 100 DEG C, and optionally a second ethylene copolymer is added to improve processability of the first ethylene alpha -olefin copolymer. The second ethylene copolymer will contain more long-chain branches than the first ethylene copolymer. The reinforcing filler is selected from talc, especially talc with a high aspect ratio, silica, or other mineral filler, or carbon black, having a strengthening effect on the film. The film will display relatively high 1 % secant modulus and a relatively high Elmendorf tear, for a film having a low Vicat softening point.
Description
The present invention relates to be used to prepare rubber mix with bag and the rubber bale packing polymeric film of being mixed; And extend to and be used for packing or splendid attire is used to add the polymeric film of the various compositions of most polymers/additive agent mixture, wherein said mixture needs lower processing temperature, and polymeric film, must be distributed in the mixture under this temperature based on the bag or the outer packaging of this polymeric film.
In the production of rubber product, elastomerics and additive (being generally the various compositions that are mixed) combination in mixing tank forms basically mixture (or rubber compound) uniformly, then it is shaped to required finished state.The mixture of this moulding can be with after fixing or crosslinked.From the economics point of rubber production, manufacturers need be mixed and be solidified quickly in order to keep competitive power.Curing means low-temperature mixed usually rapidly, and this has limited mixing temperature, because mixing temperature should not surpass the activation temperature of solidifying agent.This trend has been facilitated the rubber bale packing and/or the application of bag that is mixed, and wherein adopts fusing or remollescent film at a lower temperature, helps film to disperse rapidly in rubber/additive agent mixture like this.The bag that is mixed can be used for the various additives of splendid attire, comprising, but be not limited to: various solidifying agent, as the sulphur and the secondary accelerator of advocating peace; Reinforcing filler and non-reinforcing filler; Softening agent is as oil and wax; Tackifier; Especially be used as the extraordinary chemical additive of coupling agent and heat, ozone, ultra-violet stabilizer; Deng.Carry the packed composition that is mixed that is used for adding hybrid technique if desired, and described processing requirement bag is easy to disperse, the mixing of other polymkeric substance and/or the operation that is mixed just are similar to elastomeric mixing so.
Relatively the direct adding mode of using " scoop " to carry out adopts the composition of weighing in advance that many advantages are arranged: 1) to improve the keeping sex work, 2) improve industrial hygiene, 3) the control loss, 4) accurately and as one man improve quality, 5) reduce labour cost.In fact, can before adding mixing tank a long time ago or just, carry out weighing/measurement.It can be the moulding-can-sealing step of simple relatively manual operations or meticulousr automatization.Under any circumstance, finally to measure packing or the packed amount of substance that is suitable for directly adding in the mixing tank.
Polyethylene film is with its usually lower cost, be used to be mixed into splitting and/or rubber bale packing by moulding, can and the ability of sealing and toughness.Be perfectly clear, obviously there are various limitations in polyethylene, has therefore limited its application.The higher melt temperature and the Vicat softening point of new LDPE (film grade) are limited in higher mixing temperature with it.For example have, ethylene-vinyl acetate (EVA) multipolymer or other ethene-polar comonomers low melting point multipolymer is arranged than the ethylene copolymer of low melting point and Vicat softening point.Recently, the low of metallocene catalyst or new LDPE (film grade) (being generally the m-polyethylene) and composition thereof have very also been used and/or have discussed.Also used additive, as low melt wax to reduce these temperature.But along with to the continuous needs of low temperature more, these methods also run into various limitations.
Here and proposed among the US 5500260 and use polyethylene and/or EVA co-polymer membrane, for patent practice, incorporate it into the present invention as a reference as the bale packing and the relevant variety of issue of bag that is mixed.This patent especially proposes, and the Vicat softening point of film must be low to moderate (also open in US 5145747) below 82 ℃, and film could suitably disperse in elastomer blends like this.
Even need obtain at a lower temperature also suitably dispersive film now,, need a kind of its fusing point to be low to moderate or be lower than the film of 75 ℃ (and Vicat softening point be low to moderate or be lower than 55 ℃) especially for some rubber stock.Require Vicat softening point even lower day by day, wherein some industry requires Vicat softening point to be low to moderate 48 ℃ at present.
But, reduction along with the Vicat softening point and the fusing point of polyethylene based film, strength property decline generally can take place in the film based on polyethylene that has this fusing point/Vicat softening point concurrently or polypropylene miser, and tend to violent decline, produce with handle, transportation and store various practical problemss of not using film relevant with bag, and after can, use film and bag the time variety of issue appears.Vicat softening point is so low, become very soft, easily extend and be clamminess as 55 ℃ films, and anti-tearing property is low usually, and these all make it be difficult to process in the preparation manipulation of packing or bag, or are further used for downstream can, storage and use.In order to remedy these low strength performances, must carefully use film and/or bag with anti-tamper to a certain extent, perhaps must use thicker film to remedy this low strength.These two kinds of compensating modes commercial all be unpractical.Thickness is greatly not only uneconomical, and can add in rubber stock and more need the dispersive film.Use anti-hard caking agent and lubricant (being generally the sesame acid amides) to overcome viscosity, especially lubricant can make bag smooth, especially can be smooth to the viscosity that is enough to slow down the film that is generated by this low melting point or softening temperature polyethylene.This smooth film is difficult to use.Anti-hard caking agent is usually used in the film industry, and its consumption can be low to moderate 1000ppm (0.1% weight), and is high to 5% weight.Lime carbonate (CaCO
3) application in this film is known as filler.Although lime carbonate can improve some performance of low melting point and/or low-dimensional card softening temperature film, but still need further to improve.
In patent PCT/US94/09988, a kind of method that addresses these problems has been proposed, wherein use the polyethylene that can produce higher film toughness to mix or co-extrusion with these low melting points.Regrettably, these polyethylene that can produce higher film toughness generally have higher melt, therefore impair the overall dispersiveness of the film that comprises them.
Therefore, a kind of polyethylene film of commercial needs preferably has than low melting point with than low-dimensional card softening temperature, and its physicals (intensity) is enough to satisfy normal transport and processing and obvious disruptive polyethylene film not.
In embodiments of the invention, by using the appropriate filler reinforcing membrane, can eliminate low melting point polyethylene membrane lower intensity usually, and can obviously not influence (rising) its fusing point and/or Vicat softening point.The general filler that uses as talcum, more preferably has the talcum of high aspect ratio, most preferably surface-treated filler or its mixture.Other filler that also can use silicon-dioxide, carbon black and have reinforced effects.Use reinforcing filler that several beneficial effects are arranged.Filler or filler mixture can make the polyethylene matrix of film harder and tough and tensile, and this can be measured by the secant modulus of film, anti-thorn and anti-tearing property.By improving rigidity and toughness, can use the film of low thickness, this has not only reduced the amount of polyethylene that adds used elastomeric matrices, but also has reduced the amount that needs the dispersive membrane substance.Reinforcing filler also can improve poly rheological property, like this, by reducing energy expenditure and improving rate of extrusion, can make the film expressing technique more economically.The ideal effect of filler depends on the amount and the kind thereof of reinforcing filler, but ideal effect appears at filler content usually for based on the 5-50% weight of polyethylene/filler mixture gross weight, during preferred 10-30% weight.Filler is different from above-mentioned anti-hard caking agent, and its content all is higher than the content of above-mentioned anti-hard caking agent.
Pass through embodiment of the present invention, have been found that, the various shortcomings of above-mentioned relevant prior art can maximum degree of falling ground reduces or eliminates by using the film of being made by at least a filler enhancing ldpe resin, the Vicat softening point that wherein is used to make the resin of film may be up to 90 ℃, and its density is preferably up to 0.915g/cm
3In addition, this film (being in softening or molten state) is compatible with rubber compound usually.The melting temperature that can reach the film of this consistency generally also makes the mixing time of rubber when being mixed shorten, and has therefore improved productivity.The low melting point of film (being lower than 100 ℃) also can flow to the rubber mixture that is mixed even can guarantee film basically in the mixing period that shortens.Molten film helps to be distributed in the rubber stock.Because the temperature of specific mixture generally is the function of mixing time, but disperses within a short period of time than the film of low melting point and/or softening temperature.These films than low melting point and/or softening temperature can make rubber manufacturers shorten mixing time.
In one aspect of the invention, provide a kind of and strengthened the polyethylene film that ethene-alpha-olefin copolymer is made by filler, wherein this film has following performance:
A) strengthening polyvinyl resin density preceding and that film forming is preceding is 0.85-0.915g/cm
3
B) strengthening preceding polyethylene melting index is 0.1-10 gram/10 minutes;
C) content of reinforcing filler is the 5-50% weight based on polyethylene filler mixture gross weight;
D) fusing point of filler reinforcing membrane is no more than 100 ℃; With
E) Vicat softening point of filler reinforcing membrane is no more than 90 ℃.
In another embodiment, can add second ethylene copolymer to improve the melt processability of first ethylene copolymer.Second ethylene copolymer can be the multipolymer of the ethylenic unsaturated ester of ethene and carboxylic acid.Second ethylene copolymer is preferably has enough degrees of branching with any polymkeric substance of the melt processable that improves first ethylene copolymer (general, but needn't be so-called " high pressure " polyethylene).In this embodiment, first ethylene copolymer, promptly the amount of ethene-alpha-olefin copolymer is the 75-99% weight of polyethylene part in polyethylene/filler mixture weight.The amount of second ethylene copolymer is the 25-1% weight based on polyethylene mixture weight." weight of polyethylene mixture " is meant, therefore this polyethylene mixture can add filler to form polyethylene/filler mixture in the polyethylene mixture in above-mentioned scope subsequently as mentioned above subsequently as the basis that adds filler.
Certain embodiments of the present invention comprise polyethylene film, its preparation method and based on the application of this film.The special performance of these films makes them be specially adapted to some and is mixed or married operation.The various performances that these films had make them be better than being used in the past this being mixed or many films of production operation.Below will be within the scope of the invention, describe some preferred film in detail, the preferred preparation method of these films and the preferable use of these films based on polyethylene/filler mixture or polyethylene blend/filler mixture.Those skilled in the art under the prerequisite that does not deviate from the scope of the invention, can carry out many improvement to these preferred embodiments as can be seen.For example, carry out illustration although can be mixed at elastomerics based on the various performances of the film of polyethylene and/or polyethylene blend/filler mixture in using, they also have many other purposes, are mixed as plastics.With regard to the specific descriptions of this paper, they only are used to illustrate the preferred embodiments of the invention, therefore should not limit the present invention in these particular.
The numerical value of the various testing method that in this paper and claim, provide, measure in the following manner:
Melting index (MI): ASTM D 1238,190 ℃ of condition E, 2.16 kilogram-masses; Be expressed as gram/10 minute.
Vicat softening point: ASTM-1525,1000 gram weight (℃).
Fusing point: dsc (DSC), the second melting curve, melting peak (℃) (ASTMD-3417).
Rigidity (modulus) ASTM D-882 (with pound/square inch expression)
Anti-tearing property (ELMENDORF) ASTM D-1922 (representing) with gram or gram/mil
Film of the present invention as the rubber bale packing or the bag that is mixed has following performance: be enough to pack the excellent sealing intensity, low melting point of the various compositions that are mixed, good sealability (comprising the thermal viscosity that is enough to be used in moulding-can-seal), low-dimensional card softening temperature, improved anti-tearing property and improved rigidity (this can be measured by the secant modulus of filler polyethylene film mixture).Low-dimensional card softening temperature and low melting point can improve and film is added rubber and/or rubber be mixed in the basic uniform mixture of composition to form the overall evenly ability of rubber compound.
Film of the present invention as the rubber bale packing and the bag that is mixed can be made by first ethylene copolymer separately, perhaps by first ethylene copolymer and one or more other ethene-alpha-olefin copolymer or make with the blend of Alathon, as long as can accept its Vicat softening point.
These ethene-alpha-olefin copolymers or its blend can mix with reinforcing filler by using mixing device (well known to those of ordinary skill in the art), obtain good filler dispersion, thereby have strengthened the film based on this polymer packing mixture.Mixing device includes, but not limited to single screw rod and twin screw extruder and various continuous mixing device.The batch-type mixing tank also is applicable to and mixes and the enhancing step.
The film of being made by ethene-alpha-olefin copolymer/filler mixture has the Vicat softening point that is lower than 90 ℃ and is lower than 110 ℃ fusing point.Preferably, the Vicat softening point of this film is lower than 80 ℃, more preferably less than 70 ℃, most preferably is lower than 60 ℃, and the DSC fusing point is lower than 100 ℃, preferably is lower than 90 ℃, more preferably less than 80 ℃.
In one embodiment of the invention, being used for the be mixed film of bag of bale packing or be used to is to be made by the mixture of polyethylene and filler.In each case, this film all must have above-mentioned softening and melting characteristic, it could be added rubber like this and be mixed in the step, and can add and obtain being mixed uniformly basically elastomer blends.
Polyethylene
The film of certain embodiments of the invention can be made by the enhancing mixture of ethene-alpha-olefin copolymer (first ethylene copolymer).The density of this first ethylene copolymer is 0.85-0.915g/cm
3, Vicat softening point is lower than 90 ℃, and dsc (DSC) secondary fusing point (fusing point) is no more than 100 ℃.The alpha-olefin that is used for preparing first ethylene copolymer is to be selected from one or more of propylene, 1-butylene, 4-methyl-1-pentene, 1-amylene, 1-hexene, 1-octene, 1-decene or its mixture.As long as fusing point and/or Vicat softening point can remain in the preferable range, also can use ethene-alpha-olefin copolymer with more than one alpha-olefins polyethylene part as polyethylene/filler mixture, this combination includes, but are not limited to: ethylene/propene; Ethene, 1-butylene; Ethene, 1-hexene; Ethene, 1-amylene; Ethene/4-methyl-1-pentene; Ethene, 1-octene; Ethene, propylene; 1-butylene; Ethene, propylene, 1-hexene; Ethylene/propene, 1-amylene; Ethylene/propene, 1-octene; Ethene and analogue.
First ethylene copolymer can prepare by many methods, comprising low-pressure process, vapor phase process, fluidized bed process, slurries or solution method.The catalyzer that is used for polyreaction is generally metallocenes-aluminium alkane, metallocenes-ionization activator or conventional metallocene type catalyzer.These catalyzer are known.Therefore, EP 1229368, United States Patent (USP) 5026798 and 5198401 disclose useful various catalyzer, in order to use United States Patent (USP), incorporate it into the present invention as a reference at this.
Be one or more second ethylene copolymers can be sneaked in first ethene-alpha-olefin copolymer or all multipolymers alternatively.The second ethylene copolymer master is if it were not for the Vicat softening point or the fusing point that are used to reduce by first ethylene copolymer, but do not get rid of this purposes.In general, second ethylene copolymer can be used for improving the melt processable (higher melt strength) of polyethylene mixture, and just is not used to improve the processibility of first ethylene copolymer.Second ethylene copolymer generally is the molecule that comprises branched structure, is typically those that make in high-pressure process well known to those of ordinary skill in the art, radical method.In another embodiment of the present invention, second ethylene copolymer is a Natene, or is preferably the ethylene copolymer of ethene and at least a ethylenically unsaturated carboxylic acids ester.Preferably ethylenically unsaturated carboxylic acids comprises, for example, and vinyl acetate, methyl acrylate, butyl acrylate, ethyl propenoate and composition thereof.Preferred ester monomer is a vinyl acetate.The amount of these comonomers in second ethylene copolymer be, based on the second ethylene copolymer gross weight 1-35% weight, and the unsaturated acrylate of preferred 1-30% weight.Also can use the mixture of these ethylene copolymers.
In general, second ethylene copolymer is to improve the ability of the first ethylene copolymer processibility and fusing point and/or Vicat softening point thereof according to it to select.That is to say, the fusing point of these polymkeric substance and/or Vicat softening point should be to the obvious injurious effects of these same parameter generating of first ethylene copolymer and the film of being made by it when adding blend, but can relax some manufacturing deficiency that is present in sometimes in first ethylene copolymer.In general, by adding second ethylene copolymer or multipolymer, the bubble stability of first ethylene copolymer or the width of cloth performance that contracts can be improved 10%." obviously injurious effects " are meant that the adding of second ethylene copolymer or multipolymer can not be elevated to fusing point and/or softening temperature more than the described preferred levels.
In the production process based on the film of above-mentioned ethene-alpha-olefin copolymer, if add second ethylene copolymer, its content is the 25-1% weight based on the polyethylene blend gross weight so.The amount of first ethene-alpha-olefin copolymer is the 75-99% weight based on the polyethylene blend gross weight.
In a preferred embodiment, the amount of first ethene-alpha-olefin copolymer is the 80-95% weight based on the polyethylene blend gross weight.The content of second ethylene copolymer is the 20-5% weight based on the polyethylene blend gross weight.More preferably, first ethene-alpha-olefin copolymer is a 85-95% weight, and second ethylene copolymer is a 5-15% weight.These weight percentage are based on the gross weight of polyethylene part in polyethylene/filler mixture.
In addition, 1% secant modulus of reinforcing membrane on vertical (MD) is preferably greater than 7000psi, more preferably greater than 8000psi, most preferably greater than 10000psi greater than 6000psi.In addition, 1% secant modulus of this film on horizontal (TD) is preferably greater than 7000psi, more preferably greater than 8000psi, most preferably greater than 9000psi greater than 6000psi.
The tearing property of Elmendorf of this film following (gram/mil):
MD TD
＞150 ＞140
Preferably＞160＞160
More preferably＞200
Most preferably＞250
Should be appreciated that, by first ethylene copolymer or at least two kinds of different ethene-alpha-olefin copolymers (as, other ethene-alpha-olefin copolymer of first ethene-alpha-olefin copolymer and one or more) film that blend is made can strengthen with filler, and do not using second ethylene copolymer, be used to make film under the situation as ethylene-vinyl acetate copolymer.Yet, under the situation that first ethylene copolymer is strengthened and use separately, or carry out under the situation of blend at first ethylene copolymer and at least a other ethene-alpha-olefin copolymer, should be appreciated that, the Vicat softening point that can comprise the gained film of filler should not surpass 90 ℃, and the fusing point of film should be above 100 ℃.
Also can consider not exist basically under the situation of ethene-alpha-olefin copolymer the film of making by ethylenically unsaturated carboxylic acids ester copolymer and disclosed filler.And, can estimate that also this film has the disclosed Vicat softening point and the fusing point upper limit, and preferably have one or more secant modulus scopes and/or tear strength scope.
In the polyethylene part of the polyethylene/filler mixture that is used for the certain embodiments of the invention film, can consider that also the blend of ethylenically unsaturated carboxylic acids ester copolymer is as main ingredient.
Therefore, these embodiments can comprise following content:
The preferred 75-100 25-0 of ethene-ethylenically unsaturated carboxylic acids ester copolymer ethene-alpha-olefin copolymer is 85-95 5-15 more preferably
The blend of not getting rid of following situation, wherein: 75-25% weight is ethene-alpha-olefin copolymer, remaining part is ethene-ethylenically unsaturated carboxylic acids ester copolymer.
In all cases, no matter the polyethylene part is blend or single polyethylene, has all constituted the polyethylene part in polyethylene/filler mixture subsequently.Can transform film forming this mixture and should have one or more described Vicat softening points, melt temperature, 1% secant modulus and/or tearing property of Elmendorf.
Filler/enhancement
Should be appreciated that polyethylene (one or more in disclosed two types of ethylene copolymers) can strengthen by several method.One of them can mix all the components (polymkeric substance, filler, lubricant, anti-hard caking agent, processing aid, stablizer etc.) that strengthens in the polymkeric substance, forms intact polyethylene/filler mixture in order to extruding film forming; Or in addition, " masterbatch " of filler and/or additive is prepared in a kind of or all multipolymers, dilute to prepare same polymeric blends with this multipolymer " discharge " or with each composition and/or the multipolymer of surplus then.Under second kind of situation, be appreciated that by thorough mixing in the film forcing machine, can obtain even matter film.
It can also be appreciated that in the film of the present invention and also can have various additives.According to those skilled in the art's understanding, these additives should comprise those additives that the thermostability etc. of film forming processibility, resin or the film of surface property to film, resin works.The additive of these and other kind is generally comprised within the polyolefine, but also can add without these polyolefin carrier.Described additive types and not meaning that is fully enumerated, and just illustrative.Be appreciated that additive contained in the film is different from the additive that is included in the component packaged bag that is mixed, though their kind can be identical or different, their end-use is different.
Reinforcing filler can be the talcum that has or do not have surface treatment agent, preferably has the talcum of high aspect ratio; Or the reinforcing filler of any other kind, comprising, but be not limited to: the various forms silicon-dioxide (fused silica, precipitated silica, etc.) that has or do not have coupling agent; Other mineral type filler, comprising, but be not limited to: other mineral type filler of kaolin and other clay, feldspar, natural and synthetic silicate, carbide filler, metal oxide, vitriol, silicate and titanate and carbon black and so on.These mineral type fillers also can comprise surface treatment agent discussed below and/or coupling agent.Other filler also has, and can improve the various fillers of rigidity and anti-tearing property, although the main application of these fillers is to influence other performance, as electroconductibility or flame retardant resistance.The steatitic surface treatment agent can be stearic acid or any other treatment agent of polyethylene affinity that is usually used in improving filler.Laminal filler is the effective diameter of sheet material and the ratio of thickness as the steatitic aspect ratio.Lime carbonate is actually spheroid, so its aspect ratio is about 1, and the steatitic aspect ratio of using in certain embodiments of the invention is about 20-50.The strength property and the rigidity of these filling films are improved, and make that packing and/or bagged product are easy to use, and have produced the dispersibility of low melting point membrane structure in machinery (rubber or elastomerics) mixing tank simultaneously.
In these preferred embodiments, preferably, reinforcing filler, as talcum, the steatitic content that preferably has high aspect ratio is the 5-50% based on polyethylene (or polyethylene blend) and filler gross weight, preferred 10-40%, more preferably 15-30%.Also can use the mixture of filler.For example, can use the mixture of lime carbonate and one or more talcums or above-mentioned other filler.These mixtures are the parts in the embodiment, as long as final polyethylene/filler mixture can satisfy required melting properties disclosed herein, softening performance and physicals.The content of reinforcing filler (% weight) is based on the weight of final and any and all additives of polyethylene or polyethylene blend.At ethene-alpha-olefin copolymer (or blend of ethene-alpha-olefin copolymer) or in the blend of ethene-alpha-olefin copolymer and at least a ethylene copolymer, the amount of reinforcing filler should be able to effectively improve the physicals of gained film, simultaneously Vicat softening point and DSC fusing point is remained in the described scope discussed above.That is, the content of filler should make film have following various performance:
Dimension card fusing point
Be lower than and ℃ be lower than ℃
90 100
Preferred 80 90
More preferably 70 80
Most preferably 60
Tearing property of modulus
Greater than ℃ greater than ℃
(Kpsi) (g/cm
3)
MD TD MD TD
6 6 150?140
Preferred 77 160 160
More preferably 88 200
Most preferably 10 9 250
In embodiments of the invention, rubber uses mechanical mixer to be mixed usually.The rubber that is mixed can comprise the mixing unvulcanized rubber that has bale packing of the present invention and/or be mixed bag composition.This rubber that is mixed also can comprise promotor, curing or linking agent, filler, tinting material, antioxidant and other auxiliary agent.
Extrude although enumerated individual layer, also can carry out multilayer and extrude.In one or more layers, the amount of filler should be enough to improve the physicals of gained film.Every layer base resin (polyethylene) or polyethylene can be identical or different.Under any circumstance, should exist the filler of significant quantity with one in the performances such as improvement film modulus, tear strength or multinomial in one or more layers.
In addition, as mentioned above, the polyethylene component of telolemma can be one or more poly blends or co-extrusion thing.For example, the blend of two kinds " ethene-alpha-olefin copolymers " can comprise ethene/1-butylene blend, and ethene/1-octene blend.These blends also can comprise (ethene/1-butylene)/ethene/1-hexene blend; Ethene/1-hexene/ethene/1-octene blend; Ternary blends as ethene/1-butylene/(ethene/1-hexene), also can use ethene/1-octene blend.
Also have, so-called " second ethylene copolymer " can be one or more multipolymers, as the ionomer of ethylene-vinyl acetate, ethylene-methyl acrylate, ethylene-propylene acetoacetic ester, the positive butyl ester of ethylene-acrylic acid, ethylene-acrylic acid, ethylene-methyl methacrylate, acid copolymer; Terpolymer is as ethylene-vinyl acetate, methacrylic acid; Ethylene-methyl acrylate, vinylformic acid; And analogue.Second ethylene copolymer can be the blend of two or more second ethylene copolymers.
According to those skilled in the art's understanding, the amount of second ethylene copolymer of optional and first ethylene copolymer blend should be able to effectively improve the processibility of first ethylene copolymer, generally is the bubble stability or the width of cloth performance (casting films) that contracts.Using second ethylene copolymer also to can be telolemma increases other character, as lower cost.
Under the situation of the processing advantage that need not second ethylene copolymer, especially, also can only use first ethylene copolymer considering to adopt filler to improve under the situation of rheological property.
At relevant " polyethylene/filler " blend films or composition in any case, being appreciated that term " polyethylene " means comprises any mixture discussed above, maybe can produce the mixture of low melting point and/or softening temperature.The amount of filler (as 5-50% weight) is based on the gross weight of polyethylene or polyethylene blend.
Embodiment 1
At diameter is that 1.5 inches, screw slenderness ratio (L/D) are that 24: 1 and film head diameter are to make film on 2 inches the Sterling blowing mould extruding production line.Exact with 87.5% weight
4011 (being produced by Exxon Chemical Co.) are made resin (polyethylene) blend that is used for film with the mixed pellet of doing of the masterbatch (in following prescription, being shown in the following all the components of Exact) of 12.5% weight.Obtaining following final mixture forms:
% weight
Exact
4011 87.50
LD?760.36 10.24
Sesame acid amides 0.375
Stearylamide 0.375
Diatomite 1.500
Dynamar
FX?9613 .009
99.999％
Exact 4011 and LD 760.36 can derive from Exxon Chemical Company.Exact4011 is that nominal density is that 0.885g/cc and melting index are butylene-ethylene copolymers of/10 minutes of 2.2 grams.LD 760.36 is that melting index is/10 minutes the EVA multipolymers that comprise 27.5% vinyl acetate of 2.3 grams.
Dynamar
FX-9613 is the fluoropolymer that derives from 3M Co., helps to eliminate melt fracture.
Embodiment 2
On the extruding production line identical, use by lime carbonate Hi Pflex with embodiment 1
100 (deriving from Speciality Minerals Corp) enhanced polymeric blends system film.This mixture is prepared in Werner Pfleider twin-spiral mixer.
% weight
Exact?4011 64.5
LD?760.36 10.0
Sesame acid amides 0.07
Dynamar?FX?9613 0.14
Ciba?Geigy?B-900 0.26
Hi?Pflex?100 25.00
99.97％
Embodiment 3
By do mixing following material, in the laboratory forcing machine identical, mix then with embodiment 1, prepare 10% talcum mixture.At this used 30%UTMT 609BF enriched material is by Speciality Minerals, in its laboratory blender, is made by the 30%UTMT 609BF among the Exact 4011.UTMT 609BF is the talcum with processing of high aspect ratio.
% weight
Exact?4011 54.5
30%UTMT 609BF enriched material 33.0
SSABC0612VA 12.5
100.0％
Gained film composed as follows:
% weight
Exact?4011 77.6
UTMT?609BF 9.9
LD?760.36 10.24
Sesame acid amides .375
Stearylamide .375
Diatomite 1.500
Dynamar?FX?9613 .009
99.999
Embodiment 4
According to the same way as of embodiment 3, prepare 20% talcum mixture by the identical enriched material (in laboratory blender, making especially) that is included in 30% talcum of handling (30%UTMT 609BF) among the Exact 4011 by Speciality Minerals.
% weight
Exact?4011 20.5％
30%UTMT 609BF enriched material 67.0
SSABC0612VA 12.5
100％
Gained film composed as follows:
% weight
Exact?4011 67.4
UTMT?609BF 20.1
LD?760.36 10.24
Sesame acid amides 0.375
Stearylamide 0.375
Dia.Earth 1.500
Dynamar?FX?9613 .009
99.999
Embodiment 5
Mix following material by doing, prepare 26% talcum mixture in a similar manner.
% weight
30%UTMT 609BF enriched material 87.5
SSABC0612VA 12.5
100.0％
Obtain:
% weight
Exact?4011 61.2
UTMT?609BF 26.3
LD?760.36 10.24
Sesame acid amides .375
Stearylamide .375
Diatomite 1.500
Dynamar?FX?9613 .009
99.999％
Contemplated embodiments 6,7 and 8
Repeat embodiment 1,4 and 5, but substitute Exact 4011 with LD 760.36.Can expect that the talcum (embodiment 7 and 8) that adds 20% weight and 25% weight can really not brought up to the Vicat softening point of resin itself more than 51 ℃.In addition, can expect secant modulus (MD﹠amp; TD) improve at least 30%, and the Elmendorf tear resistance is significantly increased.
Table 1
Contemplated embodiments embodiment 12345678 fillers do not have CaCO
3Talcum talcum talcum does not have talcum talcum % weight 0 25% 10% 20.1% 26.3% 0 20% 25% thickness, mil 1.73 2.10 2.0 1.9 1.95 2.0 2.0 2.0 secant modulus, psi
MD 6590 8630 8063 12400 13080
TD 3,500 4,870 9,197 10870 11870Elmendorf tear, gram
MD 229 356 253 539 337 (gram/mil) 132 169.5 126.5 283.6 172.8
TD 218 386 305 607 606 (gram/mil) 126 183.8 1,525 319.5 310.7 power, ampere 33 35 30 25 23 bubble stabilities the highest minimum DSC fusing point, ℃ 71.5 72.5 72.7 72.5 73.5Vicat softening temperatures, ℃ 56.4 56.4 55.1 53.7 49.4 51＜55＜55
------------------
Table 1 shows that along with the adding of reinforcing filler, wonderful variation has taken place the physicals of embodiment 1-5.By using lime carbonate, the rigidity of embodiment 2 and tear strength are better than embodiment 1, and the DSC fusing point does not have obviously to raise, and Vicat softening point does not change because of obvious enhancement.In embodiment 3,4 and 5, steatitic uses and has produced higher enhancement astoundingly, and this can find out by the significantly rising of rigidity (secant modulus) and the rising at double of anti-tearing property.In addition, processing characteristics improves along with the adding of reinforcing filler, and this can find out by the reduction of watt consumption and the raising of bubble stability.It is highly important that vicat softening point temperature reduces along with the rising of talc content, this shows, is improving the matrix flexible simultaneously, and matrix is more prone to disperse.
Sum up
By some preferred embodiment of reference the present invention, the present invention has been carried out quite detailed description, but also can have other embodiment.For example, though illustration be used for rubber bale packing and the film that is mixed into splitting by what polyethylene-talcum mixture was made, can consider other purposes.Therefore, the purport of claims and scope should not be limited to the description content of the preferred embodiment of the invention.
Claims (12)
1. film that is used for the batch of material packing bag, its Vicat softening point is lower than 90 ℃, and fusing point is lower than 100 ℃, and 1% secant modulus is greater than 10000psi (MD) and 6000psi (TD), and Elmendorf tear strength (gram/mil) is greater than 150 (MD) and 200 (TD), and it comprises:
A) at least the first ethene-alpha-olefin copolymer, the density of described first multipolymer is lower than 0.915g/cm
3With
B) talcum of 5-50% weight, described weight percentage is based on the gross weight of ethene-alpha-olefin copolymer.
2. according to the batch of material packing bag of claim 1, wherein: the Vicat softening point of described film is lower than 80 ℃, preferably is lower than 70 ℃, more preferably less than 60 ℃; Fusing point is lower than 90 ℃, preferably is lower than 80 ℃, more preferably less than 80 ℃; 1% secant modulus greater than 7000psi (MD) and (TD) is preferably greater than 8000psi (MD) and (TD), more preferably greater than 10000psi (MD) and 9000psi (TD); And the Elmendorf tear strength greater than 160 gram/mils (MD) and (TD), is preferably greater than 200 gram/mils, more preferably greater than 250 gram/mils.
3. according to any one batch of material packing bag in the aforementioned claim, wherein said ethene-alpha-olefin copolymer is a kind of in ethene/1-butylene, ethene/1-hexene, ethene/1-octene or its mixture, and the density of described multipolymer is lower than 0.910g/cm
3Wherein said talcum is a kind of in talcum, high aspect ratio talcum, surface-treated talcum, surface-treated high aspect ratio talcum or its mixture, and the amount in described film is the 10-40% weight based on described ethene-alpha-olefin copolymer gross weight, preferred 15-30% weight.
4. according to any one batch of material packing bag in the aforementioned claim, wherein said film also comprises the ethylenically unsaturated carboxylic acids ester copolymer.
5. according to any one batch of material packing bag in the aforementioned claim, wherein said film also comprises lime carbonate.
6. packing comprises:
A) a kind ofly be the be mixed article of composition or its mixture of unvulcanized rubber, vulcanized rubber, rubber, wherein said article tunicle covers or contacts with film;
B) Vicat softening point of described film is lower than 70 ℃, 1% secant modulus (MD﹠amp; TD) greater than 8000psi, the Elmendorf tear strength is greater than 150 gram/mils (MD) and 200 gram/mils (TD), and described film comprises:
I) first ethene-alpha-olefin copolymer of ethene and one or more alpha-olefins at least, described alpha-olefin are a kind of in 1-butylene, 1-hexene, 1-octene or its mixture, and the density of described multipolymer is lower than 0.910g/cm
3With
Ii) filler, the amount of described filler in described film is at least 10% weight based on described ethylene copolymer gross weight.
7. according to the packing of claim 6, wherein said filler is a kind of in talcum, surface-treated talcum, high aspect ratio talcum, high aspect ratio surface-treated talcum, feldspar, silicon-dioxide, metal oxide, vitriol, silicate, titanate or its mixture.
8. according to the packing of claim 6, wherein said filler is a kind of in the surface-treated talcum of talcum, surface-treated talcum, high aspect ratio talcum, high aspect ratio or its mixture.
9. according to the packing of claim 6, wherein said film comprises:
A) polyethylene or polyethylene blend; With
B) filler of significant quantity makes 1% secant modulus (MD﹠amp of described film; TD) be at least 10000psi (MD) and 9000psi (TD), and the Elmendorf tear strength is at least 160 gram/mils (MD) and 200 gram/mils (TD).
10. packing according to Claim 8, wherein said polyethylene is an ethylene/alpha-olefin copolymer, wherein said alpha-olefin is a kind of in propylene, 1-butylene, 1-amylene, 4-methyl-1-pentene, 1-hexene, 1-octene or its mixture, and the density of described multipolymer is lower than 0.910g/cm
3
11. packing according to Claim 8, wherein said polyethylene also comprises second ethylene copolymer, comonomer in wherein said second ethylene copolymer is a kind of in vinyl acetate, methyl acrylate, ethyl propenoate, n-butyl acrylate, vinylformic acid, methacrylic acid or its mixture, and the amount of wherein said second ethylene copolymer is the 1-25% weight based on the ethylene copolymer gross weight.
12. packing according to Claim 8, wherein said filler are a kind of in the surface-treated talcum of talcum, surface-treated talcum, high aspect ratio talcum, high aspect ratio or its mixture.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US76162696A | 1996-12-05 | 1996-12-05 | |
| US08/761,626 | 1996-12-05 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1239973A true CN1239973A (en) | 1999-12-29 |
Family
ID=25062798
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97180326A Pending CN1239973A (en) | 1996-12-05 | 1997-12-05 | Dispersible film |
Country Status (10)
| Country | Link |
|---|---|
| EP (1) | EP0941277A1 (en) |
| JP (1) | JP2001505610A (en) |
| KR (1) | KR20000057382A (en) |
| CN (1) | CN1239973A (en) |
| AU (1) | AU5791898A (en) |
| BR (1) | BR9713688A (en) |
| CA (1) | CA2269672A1 (en) |
| IL (1) | IL129611A0 (en) |
| NO (1) | NO992698L (en) |
| WO (1) | WO1998024834A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102206375A (en) * | 2011-04-29 | 2011-10-05 | 南通德明塑胶新材料有限公司 | Nano calcium carbonate low melting point plastic film and manufacturing method thereof |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060086455A1 (en) * | 2004-10-27 | 2006-04-27 | Larry Laurenzi | Method of labeling rubber component bags |
| US7439306B2 (en) | 2004-11-23 | 2008-10-21 | Exxonmobil Chemical Patents Inc. | Polyethylene blends with improved Vicat softening point |
| WO2016190373A1 (en) * | 2015-05-28 | 2016-12-01 | 三洋化成工業株式会社 | Curable resin composition and method for producing same |
| AR107047A1 (en) | 2015-12-22 | 2018-03-14 | Dow Global Technologies Llc | PACKAGING FILM |
| BR112020003678B1 (en) | 2017-08-23 | 2024-03-05 | Dow Global Technologies Llc | COMPOSITION, FILM AND ARTICLE |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0385599A3 (en) * | 1989-02-13 | 1992-08-05 | Exxon Chemical Patents Inc. | Film and polymer composition for film |
| US5525659A (en) * | 1993-09-08 | 1996-06-11 | The Dow Chemical Company | Batch inclusion packages |
| US5415905A (en) * | 1993-09-29 | 1995-05-16 | Exxon Chemical Patents Inc. | Dispersible film |
| JP3372130B2 (en) * | 1995-05-12 | 2003-01-27 | 三井化学株式会社 | Rubber wrapping film and rubber veil |
| KR100222350B1 (en) * | 1995-10-09 | 1999-10-01 | 나카히로 마오미 | Polypropylene resin composition for exterior parts of an automobile |
-
1997
- 1997-12-05 BR BR9713688-3A patent/BR9713688A/en not_active Application Discontinuation
- 1997-12-05 CA CA002269672A patent/CA2269672A1/en not_active Abandoned
- 1997-12-05 KR KR1019990704931A patent/KR20000057382A/en not_active Application Discontinuation
- 1997-12-05 WO PCT/US1997/022069 patent/WO1998024834A1/en not_active Application Discontinuation
- 1997-12-05 JP JP52575398A patent/JP2001505610A/en active Pending
- 1997-12-05 EP EP97954039A patent/EP0941277A1/en not_active Withdrawn
- 1997-12-05 CN CN97180326A patent/CN1239973A/en active Pending
- 1997-12-05 AU AU57918/98A patent/AU5791898A/en not_active Abandoned
- 1997-12-05 IL IL12961197A patent/IL129611A0/en unknown
-
1999
- 1999-06-03 NO NO992698A patent/NO992698L/en not_active Application Discontinuation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102206375A (en) * | 2011-04-29 | 2011-10-05 | 南通德明塑胶新材料有限公司 | Nano calcium carbonate low melting point plastic film and manufacturing method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| NO992698D0 (en) | 1999-06-03 |
| BR9713688A (en) | 2000-03-28 |
| NO992698L (en) | 1999-07-19 |
| CA2269672A1 (en) | 1998-06-11 |
| AU5791898A (en) | 1998-06-29 |
| EP0941277A1 (en) | 1999-09-15 |
| IL129611A0 (en) | 2000-02-29 |
| KR20000057382A (en) | 2000-09-15 |
| WO1998024834A1 (en) | 1998-06-11 |
| JP2001505610A (en) | 2001-04-24 |
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