CN1225056A - Metallized multilayer packaging film - Google Patents
Metallized multilayer packaging film Download PDFInfo
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- CN1225056A CN1225056A CN 97196223 CN97196223A CN1225056A CN 1225056 A CN1225056 A CN 1225056A CN 97196223 CN97196223 CN 97196223 CN 97196223 A CN97196223 A CN 97196223A CN 1225056 A CN1225056 A CN 1225056A
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Abstract
A metallized multilayer film comprising a film substrate having a polymer core layer, e.g., a polypropylene homopolymer (OOP), on at least one surface of which is a polymer skin layer having a lower melting temperature than that of said core layer, the exposed surface of skin layer having been treated prior to coating to increase its adherence to other materials, the film substrate containing a metal deposit, e.g., aluminum, coated on the treated surface of the polymer skin layers, and a polymeric, low temperature sealable coating (LTSC) comprising a copolymer of 10 to 35 wt.% of at least one alpha, beta-ethylenically unsaturated carboxylic acid, e.g., acrylic or methacrylic acid, with 65 to 90 wt.% of ethylene, an alkyl acrylate or methacrylate, acrylonitrile, or mixtures thereof on the surface of the metal deposit.
Description
The present invention relates to metallized multilayered packaging film, they are used to packaged food or non-food stuff product or are used to form bag, carton or the bag shaped device of placing food.
United States Patent (USP) № 4345005 discloses a kind of oriented polypropylene films, and it has the adhesion that metallized coating is had increase.It is made by following steps: co-extrusion has polypropylene homopolymer sandwich layer and the outer field film substrate of ethylene/propene copolymer, and film is carried out biaxial orientation, and skin is carried out Corona discharge Treatment.Metal coating can be deposited on then on the layer of Corona discharge Treatment.
United States Patent (USP) № 4692380 discloses the polypropylene film of metallized biaxial orientation.They are made by following steps: co-extrusion is as the polypropylene homopolymer that contains the fatty acid amide slipping agent of sandwich layer and the propylene/ethylene copolymer that forms thin layer on a surface of polypropylene sandwich layer, the propylene/ethylene layer is carried out Corona discharge Treatment, make surface metalation through Corona discharge Treatment.
But United States Patent (USP) № 5126198 discloses the plural layers of hot laminatings, this film comprise one deck polypropylene based layers and at least one deck contain the extra play of the mixture of ethylene and ethylene/acrylic acid copolymer.
The metallized plural layers that are applicable to packaging applications that provided, be included on its section and have core polymer layer, lip-deep at least one of sandwich layer is the film substrate of the epidermal area of polymer, this polymer skin layer has the melt temperature that is lower than core layer polymer, the exposed surface of described epidermal area coated with increase its to the adhesion of other materials before through for example flame or Corona discharge Treatment, but such film substrate contains the coating (LTSC) that metal level for example is deposited over the lip-deep aluminium lamination of epidermal area and the low temperature involution of described processing, this coating comprises the α of 10～35% (weight), the ethene of β-ethylene linkage unsaturated carboxylic acid and 65～90% (weight), the acrylic or methacrylic acid alkyl ester, the copolymer of acrylamide or their mixture, this coating is by direct, that is, be deposited on without priming coat on the exposed surface of this metal level.
Have now found that film of the present invention is suitable for packaging applications, but the coating of metal level with good involution to metal adhesion and high sealing strength protected and is unlikely destroyed in the case.
The core layer polymer of film of the present invention generally has necessary or desirable mechanical strength in film.In many cases, to be a kind of fusing point be for example at least 125 ℃ or up to the polymer of for example 190 ℃ and higher crystallinity for such polymer.The desirable especially polyolefin that constitutes sandwich layer is isotactic polypropylene homopolymer, and for example, it is 93～99% isotactic and has 70～80% degree of crystallinity and for example 145 ℃ or up to the isotactic polypropylene homopolymer of 167 ℃ of fusing points.
Another kind of to be suitable for the polymer of making film sandwich layer of the present invention be high density polyethylene (HDPE) (HDPE), and it is essentially the polymer of straight chain, and having density for example is 0.952～0.962g/cc, fusing point be for example 130～148 ℃ with high degree of crystallinity.
It is desirable for that to produce after standing as single shaft described in hereinafter or biaxial orientation be opaque film, microballoon can be scattered in the core layer polymer by before extrusion molding and the orientation optionally at film.Such microballoon is higher than core layer polymer by a kind of fusing point and forms with the immiscible material of core layer polymer, and it can be a kind of material described in United States Patent (USP) № 4377616 and 4632869.Microballoon can be by polymer for example polyester such as polybutylene terephthalate (PBT) or PET (PET), nylon, and acrylic resin, polystyrene forms, or for example glass, metal or pottery are formed by inorganic material.Preferred micro-sphere material is PBT.The particle diameter of microballoon can be, for example, and 0.1～10 micron, be preferably 0.75～2 micron.The amount of microballoon in sandwich layer, in the gross weight of sandwich layer, can be up to 20%, be preferably 6～12%.For the structural integrity of the sandwich layer that keeps containing microballoon, can not contain the core layer polymer thin layer of microballoon at co-extrusion pressure one deck on the one side of the core layer polymer that contains microballoon or two.In the case, the polymeric layer that contains microballoon can be regarded as the whole sandwich layer of film with the polymeric layer that does not contain microballoon, and is to have the epidermal area that adjoins that the adhesion of other material is greater than sandwich layer on its each face.When such polymer architecture is carried out single shaft to or during biax orientation, around each particulate, form cavity, thereby obtain having the oriented film of opaque outward appearance.
One or two epidermal area polymer that the surface is adjoined mutually with sandwich layer are preferably extrudable hydrocarbon polymer, for example have low fusing point as than the fusing point of core layer polymer low at least 5 ℃ and 50 ℃ polyolefin the most just.The polymer that is suitable for comprises isotactic polypropylene homopolymer, propylene and for example one or more different 1-alkene of 1～10% (weight) such as ethene or for example have the isotactic copolymer of the senior 1-alkene of 4～8 carbon atoms on a small quantity.Particularly suitable be to be for example isotactic copolymer of the vinyl monomer of 1～5% (weight) of copolymer by propylene monomer and its amount, in copolymer, also can contain its amount and be for example butylene of 0.5～5% (weight).When core layer polymer is isotactic polypropylene homopolymer, as other polymer of the epidermal area of film substrate be, for example, high density polyethylene (HDPE) (HDPE), and straight-chain low density polyethylene (LLDPE).If core layer polymer is HDPE, can be any previous disclosed polymer except HDPE itself with epidermal area polymer that sandwich layer adjoins mutually, condition is that the fusing point of this polymer is lower than the HDPE that constitutes sandwich layer.Each polymer of epidermal area can be identical or inequality.
Described film normally prepares by these polymeric layers of co-extrusion pressure.After using conventional extrusion process extruding counterdie base material, film is heated and with vertically, i.e. machine direction and can also carry out molecularly oriented with horizontal direction.This single shaft to or biax orientation improve the toughness and the tensile strength of film greatly, it is to follow down at machine direction oriented film 3-8 doubly by utilizing common process to be 100 ℃～200 ℃ in the traction temperature, and can at cross directional stretch film 5-12 doubly obtain.Under most situation, the co-extrusion film with polypropylene homopolymer sandwich layer is a biax orientation, and the film with LDPE sandwich layer is a single shaft to orientation, that is, only be orientated in machine direction.
For some purpose, may wish to comprise sandwich layer and polymeric substrate with one deck or two layers of epidermal area that adjoins by casting film method or chill roll extrusion rather than co-extrusion pressure and alignment method production.In the case, final polymeric substrate is non-oriented basically, and final metallized film in general its toughness be that the film produced by co-extrusion pressure and alignment method is much lower than its base material.
Execute before metal, primer or polymerization film formation be coated with the surface of expecting film substrate applying, to the predetermined surface of accepting metal coating and can handle guaranteeing that each coating can adhere on the film substrate firmly, thereby reduce the possibility that coating shedding or film are peeled off to its reverse side.This processing can promptly, be exposed to film in the gas phase chlorine by using for example film chlorination of known method of prior art, and with oxidant for example chromic acid, hot-air or steam treatment, flame treatment, Corona discharge Treatment wait and realize.The flame on surface or Corona discharge Treatment are representational in producing film of the present invention.
Galvanoplastic or spattening finishing apply and to execute metal level and normally finish, though for example also can use the additive method of prior art by the vacuum deposition method of habitually practising to the treatment surface of film substrate.Aluminium is to be used for this purpose preferred material, also can use similar other metals that can be deposited well known in the prior art for example gold, zinc, copper, silver etc. to some purpose.
But in low temperature involution coating (LTSC), unsaturated carboxylic acid can be, for example, and acrylic acid, methacrylic acid, maleic acid, crotonic acid, itaconic acid, citraconic acid or their mixture.Usually, this copolymer is a kind of 65～90% (weight), be more typically the ethene of 75～85% (weight), with 10～35% (weight), be generally the copolymer (the former is called as the EAA copolymer, and the latter is called as the EMA copolymer) of the acrylic or methacrylic acid of 15～25% (weight).The number-average molecular weight of copolymer (Mn) is, for example, and 2000～50000, be preferably 4000～10000.
But in being applied to the low temperature involution coating of metalized surface, the polymers of carboxylic acid normally solution or the fine dispersions form of the ammonium salt of the copolymer of conduct in ammonia spirit obtains.When copolymer was dried, ammonia was evaporated and Ionized and water sensitivity carboxylate radical is converted to unionization basically and the free carboxy water sensitivity difference.Can be with a certain amount of at least a metal ion that is selected from periodic table I a, II a or the II b class, be preferably sodium, potassium, lithium, calcium or zinc ion, most preferably be sodium ion, for example their hydroxide form adds in the solution or dispersion of ethylene copolymer.The amount of said metal ion can be in being enough to neutralized copolymer total carboxylic acid's root for example 2～80%, be preferably in the scope of 10-50%.Have now found that the existence of such metal ion can cause in many cases to for example improvement of coefficient of friction (COF), thermal viscosity and pressure viscosity of some character, and can not be difficult to damage other character, for example low minimum involution temperature with accepting.(MST)。
But the polymer in the involution coating that is applied to metalized surface is acrylic acid EAA copolymer of the ethene and 20% (weight) of 80% (weight), and when the metal ion of neutralization is the sodium ion that adds with the NaOH form, so corresponding to the dosis neutralisata of carboxylate radical of the aforementioned percentage of neutralization, the addition of its NaOH can be, for example, 0.33～8.8phr, be preferably 1.1～5.5phr, " phr " represents the weight portion of each hundred parts of total resin herein, and the weight of said total resin is not identical with the weight of EAA copolymer when having other resin.In order to measure the phr of various additives in coating, the whole carboxylate radicals in the ethylene copolymer are assumed to be it is its non-free carboxy (form COOH).
Except carboxylic basic copolymer, but the involution coating that is applied to metalized surface also contains the wax of dispersion, and for example, the Brazil wax of greater particle size or microcrystalline wax are as the resistance to compression stick.Spendable other wax is, for example, and native paraffin such as paraffin, beeswax, Japan wax, montan wax or the like, and synthetic wax such as rilanit special, unichlor, long chain fatty acids amides or the like.In coating the amount of wax can for, for example, 2～12phr, be preferably 3～5phr.
Except playing the sticking material of resistance to compression, when being incorporated in the coating of the present invention, also works by wax " cold cunning " effect that improves its coated film, that is, and the ability that can slide satisfactorily across the surface of film at room temperature.
But the involution coating that is applied on the metalized surface of film also can contain granular materials, and for example, amorphous silica is so that further reduce coating viscosity at room temperature.Amorphous silica is made up of the particle that becomes as less particle agglomeration, and its average grain diameter is, for example, and 2～9 microns, be preferably 3～5 microns, but and can in involution coating, exist, its amount is, for example, 0.1～2.0phr, is preferably 0.2～0.4phr.
But can be included in other additive that can also have in the involution coating of the metalized surface that is applied to film, the granular materials that comprises other is such as talcum powder, and its amount for example is 0～2phr; Crosslinking agent such as melamine resin, its amount is for example 0～2phr; Antistatic additive is as poly-(oxygen ethene) dehydrated sorbitol mono-fatty acid ester, and its amount for example is 0～6phr.Can also there be antiseptic.
But except the low temperature involution coating on the metalized surface of film as discussed previously, can also be with the polymer film forming applying coating to the film surface opposite with metalized surface.Yet, in order to ensure of the adhesion of this coating to the described opposed surface of film substrate, at first primer is coated on this surface, this both can after this lip-deep epidermal area is processed with its bonding force of further increase to other material, also can be without such processing.The primer that is suitable for is known in the art, and comprises, for example, and the product of the polyvinyl of titanate esters, poly-(inferior ethene acid imide) and epoxy resin and aminoethylization.Primer is applied to the treatment surface of film by habitual solution coat method.Especially effectively primer of the present invention is poly-(inferior ethene acid imide), it both can be used as water or organic solvent, and for example the solution of ethanol is coated, the solution that also can be used as in the mixture of water and other organic solvent is coated, and above-mentioned solution contains the acid imide of 0.5% (weight).
But be applied to film the metalized surface reverse side contain the lip-deep coating of primer can be as with the involution coating that is applied to the coating same type on the metalized surface, perhaps it can be the polymer film forming coating of any other type as known in the art.A kind of coating of particularly suitable is the coating that contains as the copolymer of film-forming components, and it comprises, in the weight of this polymer (" acrylic ternary copolymer "), 1) at least a C of 18～80% (weight)
1～C
4Alkylmethacrylate, 2) at least a C of 18～80% (weight)
1～C
4Alkyl acrylate and 3) at least a α of 1～15% (weight), β-ethylene linkage unsaturated carboxylic acid; And as the colloidal silica of hot slipping agent, its amount is for example 3～60phr, and its particle diameter is for example 10～200 microns.But the unsaturated acids of acrylic ternary copolymer can be the unsaturated acids of the copolymer in any previous disclosed low temperature involution coating that is suitable on the metalized surface that is applied to film, though acrylic acid and/or methacrylic acid are preferred.This copolymer can be used as the aqueous solution or the dispersion of part neutralization, that is, and and latex and be used for coating composition.In coating composition, can there be additive, but these additives on the property quality and quantity be with the previous disclosed low temperature involution coating that is applicable to the metalized surface that is applied to film in those additives same or analogous, for example Brazil wax and talcum powder of wax particularly, Brazil wax plays resistance to compression stick and cold slipping agent effect, and talcum powder plays super fatting agent.This type of composition is disclosed in, for example, and among the United States Patent (USP) № 3753769 and 4749616.
It is another kind of that can be applied to film and the lip-deep polymeric coatings metalized surface opposition side with primer be a kind of such coating, wherein film-forming components is a kind of vinylidene chloride that comprises at least 50% (weight), is preferably the vinylidene chloride of 75～92% (weight), the α of 2～6% (weight), but any in those acid of the copolymer in for example previous disclosed suitable work involution coating of β-ethylenic unsaturated acid, and surplus is C
1～C
4The polymer of alkyl acrylate or methacrylate or propylene acyl cyanide.In these coating, can also exist and the previous described same or analogous additive of those additives in other coating.The aqueous solution or dispersion that vinylidene chloride copolymer can be used as the part neutralization are used.This type of coating is disclosed among the United States Patent (USP) № 4944990.
For example but desired low temperature involution coating (LTSC) composition is coated to the metalized surface of thin polymer film in any suitable manner by grooved roll coating, roller coat, dipping, spraying etc., and if you are using, primer and polymer coating are coated to opposite surfaces.The too much aqueous solution can be removed by compression roller, scraper etc.Coating composition is normally coated with such amount, so that at the level and smooth and equally distributed layer that is deposited as/1000 square inches of one deck 0.2～1 grams after the drying on film surface.In general, the thickness of coated LTSC is can give the substrate polymer film fully with desirable involution, coefficient of friction (COF) and hot smooth property.
In case coating is applied to after the film, carry out drying then by hot-air, radiant heat, or by any other appropriate method, form the coating film product of the gloss of the water-fast adhesion that for example can be used as packing film thus.
Use for example conventional solvent-based ink composition the ink logo of printing to be printed on any one surperficial coating of film, or print on the reverse side of uncoated of metalized surface, if uncoated coating on this reverse side.The pattern of printing can cover destroyed to prevent pattern with the capping lacquer.Capping lacquer can cover the whole surface that comprises printed patterns, and wherein surperficial involution is that the polymer skin layer on the film reverse side on the film portion of the adventitia that seals by softening coating or formation reaches fully.Yet, if " interior to outside " involution is still desireed, wherein involution also can be realized by softening in lip-deep coating that comprises the printing-ink pattern or polymer skin layer, the coating of a part or polymer skin layer constitute the interior film that seals, print then and at pattern middle cover finish paint Lacquer finish, so that make coating or polymer skin floor be exposed to the involution district.
Another film (" laminate film ") can also be laminated on the surface that does not apply capping lacquer metallized film of the present invention, so as to improve mechanical performance for example tearing strength and machining property, increase toughness, protect printed patterns and/or the vacuum seal of metallized film be provided.So, but laminate film can be glued on the metalized surface of film of the present invention or its reverse side on the coating of involution on, this both can be after but printed patterns be printed on the involution coating or had to carry out under the situation of such printed patterns, but perhaps under situation, laminate film is adhered to said reverse side without any the involution coating.Laminate film can comprise, for example, polymer such as isotactic polypropylene homopolymer with excellent mechanical properties, it is to be used as the molten polymer of adhesive and to be adhered on the film of the present invention, this molten polymer than laminated polymer for example low density polyethylene (LDPE) (LDPE) have lower fusing point; Perhaps laminate film can comprise the main stor(e)y of this polymer with premium properties and have the polymer sublevel that fusing point is lower than the low melting glass of main stor(e)y polymer, and laminated be that surface by being high enough to give the laminate film of sublevel polymer will contain described sublevel under the condition of viscosity in temperature is to the incompatible realization of required surface pressure of metallized film of the present invention.For realizing that described bonding necessary method and apparatus is known in the art.
Embodiment
Extrude three-layer thin-film, its sandwich layer is commercially available Fina 3371 isotactic polypropylene homopolymers, it on a surface of sandwich layer the co-extrusion epidermal area of HDPE, it on another surface of sandwich layer the co-extrusion epidermal area of isotaxy terpolymer, this isotaxy terpolymer comprises the above propylene of 90% (weight) and respectively is the ethene and the butene-1 of 1～5% (weight), and its commercial goods is called Chisso 7780.The HDPE epidermal area is to have the high stable agent to prevent the HDPE masterbatch of gelling by the commercially available Exxon HX 0353 pure HDPE of 97.5% (weight), 0.5% (weight) with the commercially available HuntsmanPolcomm A27527 fluoropolymer polymer that prevents to sting mould and 2.0% (weight).
The coextrusion thing is quenched to-50 ℃ at 30 ℃, reheats 115 ℃ and also use conveying roller to stretch 5 times in machine direction to move under the friction speed.After required machine direction stretched, film was orientated with 8 times of cross directional stretch, and suitable Temperature Distribution scope is 155 ℃～180 ℃.
It is 70ga. (gauge that the film substrate that makes has total optical measurement thickness, 1/100 mil), its sandwich layer (layer B) thickness is 62ga., and HDPE epidermal area (layer A) thickness is 2ga., and propylene/ethylene/butene-1 terpolymer epidermal area (layer C) thickness is 6ga..Subsequently the HDPE epidermal area being carried out flame treatment and be metallized by the aluminium vacuum moulding machine under standard conditions, is 2.3 high-quality isolation to provide aluminum metallization to reach optical density (OD).
In order to be coated to the metalized surface of film, but a kind of involution coating composition is by (this copolymer is made up of the acrylic acid of the ethene and 20% (weight) of 80% (weight) to the copolymer ammonium salt aqueous solution of 25% (weight) or water fine dispersions, sell with MichemPrime 4983 EAA by Michelman company) add the NaOH (NaOH) of 1.5phr (parts by weight of per hundred parts of copolymers), the Brazil wax of 4phr (selling with MichemLube 215) by Michelman company, 0.4phr talcum powder and the amorphous silica of selling with Syloid 42 of 0.3phr prepare.Each all components all is added with aqueous dispersion or solution form.Adding water then, to make the solids content of final coating composition be 12% (weight).
Under the situation of not using primer, use standard concave grooved roller and apparatus for coating and technology that coating composition is coated on the metalized surface of film, and at 240 dry coatings.In the total coating weight of dry back on film is/1000 square inches of films of 0.65 gram.
At first the metalized surface reverse side and untreated surface that contain the film substrate of propylene/ethylene/butene-1 terpolymer are used in poly-(inferior ethene acid imide) solution priming operation of 0.5% (weight) in the mixture of ethanol of water and 15% (weight) of 85% (weight).Surface to priming operation applies with following composition then, and said composition comprises the terpolymer of methyl methacrylate, ethyl acrylate and methacrylic acid, the aqueous dispersion of colloidal silica and Brazil wax or solution; Total solids content is 13% (weight), and described in United States Patent (USP) № 2753769, coating amount is/1000 square inches of films of 0.6 gram, uses the recessed roller coating device and the technology of standard, and 240 ℃ of dryings.
The coating film of this embodiment is carried out permeable vapor rate (WVTR) measure (unit is/100 square inches/day of grams) under 100 and 90%R.H.; Under 73 and 0%R.H., carry out oxygen transmission rate (OTR) and measure (unit is CC/100 square inch/sky); Measure with metallization HDPE (A) layer and reach the flat minimum involution temperature (MST, unit are F) of sealing of 100 gram/inches; At 20psi, 0.75 second and 260 ripple sealing-strengths (CRIMP) of measuring metallization HDPE (A) layer down.
With these characteristic values of measuring with from identical but on two surfaces the measured value of the tester of uncoated film compare, its result is shown in the following table.
Coating film uncoated film tester OTR 1.51 2.87WVTR 0.008 0.012CRIMP 493 of table mensuration project present embodiment is involution MST 209 involution not
Seen in from last table, in single film, can reach the good water vapor barrier and the oxygen barrier and involution of appropriateness.This structure itself can be used to replace paper/polymer/metal paper tinsel/polymer architecture (but have the metallization outward appearance, because counterdie is transparent) or be used for laminated and provide have in the film of more toughness of (the with locked in print) of seal or a thicker sealant.
Claims (8)
1. metallized plural layers, comprise film substrate, film substrate has core polymer layer, on at least one surface of sandwich layer, be the epidermal area of polymer, this epidermal area polymer has the melt temperature that is lower than core layer polymer, the exposed surface of described epidermal area had passed through processing with its adhesion to other materials of further increase before coated, but this film substrate contains the lip-deep metal level of the epidermal area that is deposited on described processing and in the lip-deep polymer low temperature of described metal deposit involution coating (LTSC), this coating comprises at least a α of 10～35% (weight), the ethene of β-ethylenically unsaturated carboxylic acids and 65～90% (weight), the acrylic or methacrylic acid alkyl ester, acrylamide, or the copolymer of their mixture.
2. the film of claim 1, wherein said sandwich layer contains second epidermal area on it contains the reverse side of metal deposit face, and second epidermal area has the melt temperature that is lower than sandwich layer.
3. the film of claim 1, wherein said core layer polymer is isotactic polypropylene homopolymer.
4. the film of claim 1, wherein said surface-treated epidermal area polymer is propylene, ethene and can also is the isotactic polymer of butene-1.
5. the film of claim 2, wherein said second epidermal area is high density polyethylene (HDPE) (HDPE).
6. the film of claim 1, wherein said LTSC copolymer is the copolymer (EMA copolymer) of ethene and acrylic acid copolymer (EAA copolymer) or ethene and methacrylic acid, and wherein 2～80% carboxylate radical is neutralized by the metal ion of the I a of periodic table, II a or II b class.
7. the film of claim 6, wherein said EAA or EMA copolymer are the copolymers of acrylic or methacrylic acid of the ethene and 15～25% (weight) of 75～85% (weight), and wherein 10～50% carboxylate radical is neutralized by sodium, potassium, calcium or zinc ion.
8. the film of claim 1, wherein said carboxylic acid ion is neutralized by sodium ion.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 97196223 CN1225056A (en) | 1996-05-07 | 1997-05-05 | Metallized multilayer packaging film |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/646,429 | 1996-05-07 | ||
| CN 97196223 CN1225056A (en) | 1996-05-07 | 1997-05-05 | Metallized multilayer packaging film |
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| CN1225056A true CN1225056A (en) | 1999-08-04 |
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| CN 97196223 Pending CN1225056A (en) | 1996-05-07 | 1997-05-05 | Metallized multilayer packaging film |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100556686C (en) * | 2002-05-11 | 2009-11-04 | 德国胡塔玛基有限两合公司胡塔玛基龙斯贝格分公司 | Plastic sheeting |
| CN101791889B (en) * | 2010-01-29 | 2012-06-27 | 浙江凯利包装材料有限公司 | Heat-resisting isolated biaxially oriented polypropylene film and manufacturing method thereof |
| CN101573231B (en) * | 2006-12-18 | 2014-04-30 | 博里利斯技术有限公司 | Terpolymer with high melting point |
| CN104968493A (en) * | 2012-11-01 | 2015-10-07 | 金达胶片美国有限责任公司 | Coated metallized oriented polypropylene films |
| CN105751626A (en) * | 2016-04-29 | 2016-07-13 | 廖雪光 | Low-temperature hot-seal spraying covering membrane |
-
1997
- 1997-05-05 CN CN 97196223 patent/CN1225056A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100556686C (en) * | 2002-05-11 | 2009-11-04 | 德国胡塔玛基有限两合公司胡塔玛基龙斯贝格分公司 | Plastic sheeting |
| CN101573231B (en) * | 2006-12-18 | 2014-04-30 | 博里利斯技术有限公司 | Terpolymer with high melting point |
| CN101791889B (en) * | 2010-01-29 | 2012-06-27 | 浙江凯利包装材料有限公司 | Heat-resisting isolated biaxially oriented polypropylene film and manufacturing method thereof |
| CN104968493A (en) * | 2012-11-01 | 2015-10-07 | 金达胶片美国有限责任公司 | Coated metallized oriented polypropylene films |
| CN105751626A (en) * | 2016-04-29 | 2016-07-13 | 廖雪光 | Low-temperature hot-seal spraying covering membrane |
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