CN103059763A - Bidirectional stretching polypropylene film for hot binding compounding, and its preparation method - Google Patents
Bidirectional stretching polypropylene film for hot binding compounding, and its preparation method Download PDFInfo
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Abstract
The invention provides a stretching polypropylene film and its preparation method. The film comprises a co-extrusion compounding base layer and a hot binding function layer, wherein the function layer comprises a component (A), or a component (B), or a mixture of the component (A) and the component (B); the component (A) is an ethylene copolymer having a polar group; the component (B) is selected from an ethylene-butylene copolymer, an ethylene-hexene copolymer, an ethylene-octene copolymer, and a mixture of the above copolymers; the ratio of the vertical elongation rate to the transverse elongation rate of the bidirectional stretching polypropylene film is less than 2; and the surface tension of the function layer of the film is in a range of 36-48dyne/cm. The invention also provides a use of the film in the preparation of film coated paper through the heating compounding with paper, and the film coated paper containing the film.
Description
Technical field
The present invention relates to plastics film product and production technique field.Concrete, the present invention relates to for and paper, the polypropylene double-way stretched film of the Material claddings such as metal and its preparation method.
Background technology
Polypropylene double-way stretched film (BOPP) has light weight, high glossiness, and height is transparent, nontoxic, moistureproof, ventilation property is low, the deflection advantages of higher, and the packing and the lamination that are widely used in the products such as food, medicine, daily light industry, cigarette are compound.BOPP film wherein a kind of purposes is to fit in paper surface, and such as books, packing carton etc. play a part moistureproof and the increase surface gloss.
Polypropylene double-way stretched film is generally the coextruded structure of 3-5 layer.The most common is 3-tier architecture, is divided into outside basic unit, sandwich layer basic unit and functional layer.Sandwich layer generally is comprised of homo-polypropylene, also can mix some functional agents, such as white master batch and pearlescent additive etc.Outside basic unit is generally homo-polypropylene and additive or delustring material and forms.It is compound that functional layer is generally used for heat posted.
Polypropylene double-way stretched film is modal to be to produce with flat embrane method two-way stretch (tenter framebi-orientation) technique, and its production technique mainly is comprised of following operation: the batching batch mixing--forcing machine is extruded--extrude sheet by T-shaped die head--sheet chilling--to sheet by warming mill preheating-sheet longitudinal stretching-heat setting type-again preheating-cross directional stretch-heat setting type-cooling-corona treatment-rolling-cut-put in storage.
BOPP important application in packing is the paper overlay film, namely by professional equipment for coating film paper printing products and BOPP Film laminated is in the same place, and forms the product of paper unification, and this technology is called film coating technique (Film lamination).Paper printing matter through overlay film, its surface is brighter, level and smooth, pattern is more bright-coloured, the performances such as wear-resisting, folding, tension, moisture-proof, resistance to chemical attack are also all strengthened, even some visual defects in printing process can be remedied to a great extent, therefore, not only prolong work-ing life, the aesthetic property of product has also improved greatly.Recombining process in the market is divided into solvent-borne type and namely is coated with technology, water-soluble technology and the precoating technology of namely being coated with.
It is that the utilization special use is that the solvent-borne type that coat film equipment will be blent through benzene solvent is that gluing is coated on the BOPP film that solvent-borne type namely is coated with technology, and drying and heating, pressurization are compound with printing.Through the packing material of overlay film, its surface-brightening, level and smooth, pattern is more bright-coloured, wear-resisting, folding, tension, moisture-proof, resistance to chemical attack.It is namely to be coated with on the basis of technology at former solvent-borne type that water-based namely is coated with technology, replaces organic solvent glue with nontoxic water-base cement (being water-based acrylic acid ester sizing agent), namely is coated with the pollution problem that technology exists thereby solve solvent-borne type.
Although water-based namely is coated with technique and has solved the benzene pollution problem that solvent-borne type namely is coated with, but there is the pollution problem after needing large water gaging cleaning and discharging cleaning sullage in it, it still not optimal environment-friendly type overlay film solution, simultaneously, water-based namely is coated with the lower problem of compound fastness that technique exists BOPP and paper, is prone to film and paper delamination in the use procedure.
Above-mentioned two kinds of BOPP namely are coated with technology and have the inefficient defective of overlay film.Owing to all need through links such as gluing, oven dry in the overlay film process, so overlay film speed is restricted, and only be 15-30 m/min, far can not satisfy high speed printing post-press finishing demand afterwards.The defective that namely is coated with technique comprises that also the applying fastness of BOPP and paper is low, and recombination process need to use environmentally harmful tackiness agent and solvent, and simultaneously, evaporating solvent can cause larger energy consumption in the glue dries process.
Disclosed among the CN2741769Y and a kind ofly be coated with one deck ethylene-vinyl acetate copolymer (EVA) raw material at the BOPP film surface by extruding, and then and the compound technique of paper heating.This film with EVA is pre-coating film.Its production process is that pre-coating film manufactory will satisfy the BOPP thin-film material of particular technology requirement, be coated with one deck EVA raw material on the BOPP surface by extrusion coated (extrusion coating).Printing packaging enterprise need not again film to be done any coating process to paper printing products overlay film process the time, only need get final product by special-purpose laminating machine heating and pressurizing.The distinctive production technique of pre-coating film and overlay film process so that its can high speed overlay film (60-100 m/min), high, the cohesive strength of compound film quality is far above namely being coated with the advantages such as technique height, overlay film post-treatment performance are good.Yet pre-coating film needs secondary in the secondary processing technique of producing good BOPP film coating one deck EVA, and the EVA price comparison is expensive.
Disclosed the compound polypropylene double-way stretched film of using of a kind of paper among the CN100566994C, this film has the top layer, sandwich layer and can forming with the functional layer that paper add thermal-adhering and form by the stretch processes time processing.This technology has overcome and existing namely be coated with the Technology Need gluing and cause potential environmental influence and can cause the larger shortcomings such as energy consumption because of evaporating solvent in the glue dries process, and the film once shaped of this technology need as pre-coating film not to need secondary in the secondary processing technique of producing good BOPP film coating one deck EVA.But this technology is because be subjected to the restriction of the film stretching adhesion in the course of processing, can not use EVA to do functional layer, and can only use the higher polyolefine of fusing point, such as ethylene-octene copolymer and co-monomer content the ethylene-butene copolymer 10%-30% between of co-monomer content at 5%-20%.These multipolymers because comonomer less, and fusing point all be higher than 95 the degree, therefore, drawing process does not have adhesion.But, defective is that temperature when adding thermal-adhering is far above existing EVA pre-coating film, not only can cause overlay film speed low, peel off fastness far below the EVA pre-coating film behind its overlay film, overlay film speed and applying fastness that the composite membrane that therefore this technology is produced can only reach and namely film suitable.
Therefore, industry member needs simple, the one-time formed BOPP film of a kind of technique, and this film has and paper applying fastness is high, and the characteristics that overlay film efficient is high can also overcome the adhesion of functional layer and processing units in the film stretching process.
Summary of the invention
The invention provides a kind of polypropylene double-way stretched film (BOPP), it comprises basic unit and the heat posted functional layer (being hot melt adhesive) of coextru-lamination.Polypropylene double-way stretched film of the present invention can be used for material heat posteds such as paper compound.Polypropylene double-way stretched film of the present invention has high transparent, high-stiffness, and with the good hot composite performance of the materials such as paper, its overlay film speed and overlay film intensity are suitable with existing EVA pre-coating film, and the time processing drawing and forming has overcome the shortcoming that the pre existing technology for coating needs secondary processing.
The invention provides a kind of polypropylene double-way stretched film, it comprises basic unit and the heat posted functional layer of coextru-lamination, polypropylene or polyethylene or its mixture are contained in wherein said basic unit, described functional layer comprises component (A) or component (B), or comprises the blend of component (A) and component (B).
Wherein, described component (A) is the ethylene copolymer with polar group, it is selected from vinyl-vinyl acetate copolymer (EVA), ethylene-acrylic acid copolymer (EAA), ethylene-methacrylic acid copolymer (EMAA), ethylene-ethyl acrylate copolymer (EEA), ethylene ionomer type polar polymer, ethene-maleic anhydride grafted polymer and its blend, described component (A) is characterised in that, test according to dsc (DSC), its fusing point is lower than about 95 degree, preferably is lower than about 90 degree.
Wherein, described component (B) is polyolefin elastomer, it is selected from ethene and butylene copolymer, ethene and hexene copolymer, ethene and propylene copolymer, ethene and octene copolymer or propylene and butylene copolymer, described component (B) are characterised in that, test according to dsc (DSC), its fusing point is lower than about 95 degree, preferably is lower than about 90 degree.
In one aspect of the invention, the longitudinal tensile strain rate of above-mentioned polypropylene double-way stretched film and the ratio of cross direction elongation are less than about 2, preferably less than about 1.5, and described film functional layer surface tension is preferably between about 36-42 dynes per centimeter between about 36-48 dynes per centimeter.
Of the present invention aspect another, above-mentioned polypropylene double-way stretched film is by periosteum method (DoubleBubble Process, being also referred to as two bubble method) stretch processes is prepared, preferred, above-mentioned polypropylene double-way stretched film is prepared by periosteum method bi-directional synchronization drawing process.
In one aspect of the invention, the functional layer of above-mentioned polypropylene double-way stretched film is measured according to dsc (DSC), the ratio that the peak area of parts that fusing point is lower than 90 degree on its DSC curve accounts for the DSC curve total area is preferably greater than about 50% greater than about 30%.
Aspect another, the ethylene copolymer with polar group described in the component (A) is vinyl-vinyl acetate copolymer (EVA) of the present invention.
Aspect another, the ethylene copolymer with polar group described in the component (A) is ethene-maleic anhydride grafted polymer of the present invention.
In one aspect, described in the component of polypropylene double-way stretched film of the present invention (A) with the ethylene copolymer of polar group (in the present invention, sometimes be also referred to as the ethene polymers with polar group) be characterised in that, maleic anhydride content is about 0.1%-2% in therein ethylene-maleic anhydride grafted polymer, therein ethylene-vinyl acetate copolymer (EVA), ethylene-acrylic acid copolymer (EAA), ethylene-methacrylic acid copolymer (EMAA), ethylene-ethyl acrylate copolymer (EEA), the poly-monomer weight content in described polar ethylene copolymer of polarity in the ethylene ionomer type polar polymer is about 5%-25%.
Of the present invention aspect another, according to the ASTMD-1238(190 degree, 2.16 kilograms) test, the melt index (MI) with the ethylene copolymer of polar group described in the component (A) is 0.5-30g/10 minute.
In one aspect, the polyolefin elastomer of component in the polypropylene double-way stretched film of the present invention (B) is the metallocene quasi-polyethylene, and it is selected from ethene and butylene copolymer, ethene and hexene copolymer, ethene and octene copolymer, and the blend of described multipolymer.In one aspect of the invention, in therein ethylene and the octene copolymer octene content greater than 20 % by weight to being less than or equal between 40 % by weight, be preferably more than 20 % by weight to being less than or equal between 30 % by weight, in ethene and the hexene copolymer hexene content greater than 15 % by weight to being less than or equal between 40 % by weight, be preferably more than 20 % by weight to being less than or equal between 30 % by weight, or in ethene and the butylene copolymer butene content greater than 15 % by weight to being less than or equal between 40 % by weight, preferred butene content greater than 20 % by weight to being less than or equal between 40 % by weight, most preferably be greater than 20 % by weight to being less than or equal between 30 % by weight.Of the present invention aspect another, described metallocene quasi-polyethylene, according to the ASTMD-1238(190 degree, 2.16 kilograms) test, its melt index (MI) is about 0.5-30g/10 minute.
In one aspect, the functional layer of the invention described above polypropylene double-way stretched film also contains polyethylene, it is selected from linear low density polyethylene (LLDPE), high density polyethylene(HDPE) (HDPE) or hp-ldpe (LDPE), and wherein said polyethylene fusing point is greater than about 100 degree.Described polyethylene accounts for the functional layer gross weight and is lower than about 40% weight, preferably be lower than about 25%, more preferably less than about 15%.
Polypropylene double-way stretched film of the present invention has one or more layers basic unit.The thermoplastic polymer with film-forming properties can be contained in described basic unit.In general, described basic unit is by forming take polypropylene as main material.Can comprise that alfon, Co-polypropylene or its blend form as the polyolefine of basic unit of the present invention film-forming polymer, typically be isotaxy homopolymer, atactic polypropylene(APP), syndiotactic polypropylene, the atactic copolymerized polypropene of a small amount of ethene or higher-alkene and the polypropylene blend of ethylene copolymer-modified isotactic polyprophlene are arranged.In basic unit, can add the additives such as other component such as petroleum resin to change such as deflection the performances such as frictional coefficient.Although be made of homo-polypropylene (Ho-PP) in the most of situation of base material, base material also can be comprised of the blend of binary or ternary polymerized polypropylene (Co-PP) or itself and homo-polypropylene.
In one aspect of the invention, according to the ASTMD-1238(230 degree, 2.16 kilograms) test, the melt index of described base material (MI) is about 0.5-15g/10 minute.
The base material material also can add the polyethylene that is selected from high density polyethylene(HDPE) (HDPE), Low Density Polyethylene (LDPE) or LLDPE (LLDPE).
HDPE not or have a small amount of comonomer does not generally have about 0.941g/cm
3Perhaps higher (about 0.952g/cm for example
3To about 0.968g/cm
3) density, about 266 ℉ are to the fusing point of about 299 ℉ (about 130 ℃ to about 148 ℃), and less than the melting index (according to ASTM D1238 measurement) of 1 to 50 gram/10 minutes (for example 1 to 50 gram is/10 minutes).
LDPE is homopolymer polymer, generally has at 0.912g/cm
3To 0.94g/cm
3(0.915g/cm for example
3To 0.928g/cm
3) the density of scope, and the melting index (measuring according to ASTM D1238) of 0.2 to 50 gram/10 minutes (for example 1 to 10 gram is/10 minutes).LDPE can use radical initiator production in high-pressure process.The LDPE of under high pressure polymerization is called as high-pressure polyethylene sometimes.
LLDPE can be divided into ethene and butylene copolymer, ethene and hexene copolymer and ethene and octene copolymer, generally have the melting index (measuring according to ASTM D1238) less than 1 to 50 gram/10 minutes (for example 1 to 10 gram is/10 minutes), and 0.910 to 0.940g/cm
3, preferred 0.915 to 0.928g/cm
3The density of scope.
Industrial have for two-way stretch BOPP film homo-polypropylene (Ho-PP) commonly used: the T38F of Lanzhou Petrochemical and Daqing petrochemical; The T36F of Dalian petrochemical industry.This class homo-polypropylene according to the ASTMD-1238(230 degree, 2.16 kilograms) test melt index (MI) can be about 0.5-15 gram/10 minutes, fusing point can be between about 155 degree-168 spend.
The additive that can add with master batch form about 0.01%-5% in the base material.Some common additives have, antiblocking agent, slipping agent, static inhibitor, nucleator etc.Base material also can comprise on a small quantity, the petroleum resin of 1%-15% for example, and petroleum resin can be low-molecular-weight, with the deflection that improves film with lower draft temperature.Petroleum resin can be through hydrotreated.Also can add the delustring masterbatch in the base material and come production delustring BOPP film.Also can add the pearly-lustre masterbatch in the base material and produce pearly-lustre BOPP film.The base material homo-polypropylene (Ho-PP) mainly provide deflection, water vapor rejection, transparency and processibility.The thickness that homo-polypropylene in the base material (Ho-PP) can account for whole film is about 50%-95%.
Outermost basic unit is also referred to as the top layer.Polypropylene described above can be contained in described top layer, can also be mixed with polyethylene in addition, the polyethylene that it is selected from high density polyethylene(HDPE) (HDPE), Low Density Polyethylene (LDPE) and LLDPE (LLDPE) for example can add high density polyethylene(HDPE).In one aspect of the invention, polypropylene and poly blend are contained in the top layer of described polypropylene double-way stretched film, and wherein said polyethylene is high density polyethylene(HDPE), and polypropylene is homo-polypropylene or Co-polypropylene.
Polypropylene double-way stretched film of the present invention also comprises the heat posted functional layer, and wherein said functional layer comprises the blend of component (A) or component (B) or its component (A) and component (B), wherein:
Component (A) is with the ethylene copolymer of polar group (in the present invention, sometimes be also referred to as the ethene polymers with polar group), it is selected from vinyl-vinyl acetate copolymer (EVA), ethylene-acrylic acid copolymer (EAA), ethylene-methacrylic acid copolymer (EMAA), ethylene-ethyl acrylate copolymer (EEA), ethylene ionomer type polar polymer, ethene-maleic anhydride grafted polymer and its blend, described component (A) is characterised in that, test according to dsc (DSC), its fusing point is lower than about 95 degree, preferably is lower than about 90 degree;
Component (B) is polyethylene elastomer, it is selected from ethene and butylene copolymer, ethene and hexene copolymer, the blend of ethene and octene copolymer and described multipolymer, described component (B) is characterised in that, test according to dsc (DSC), its fusing point is lower than about 95 degree, preferably is lower than about 90 degree
Wherein, the longitudinal tensile strain rate of described polypropylene double-way stretched film and the ratio of cross direction elongation be less than about 2, and preferably less than about 1.5, and described film functional layer surface tension is preferably between about 36-42 dynes per centimeter between about 36-48 dynes per centimeter.
In one aspect, be characterised in that with the polyvinyl of polar group described in the component of polypropylene double-way stretched film of the present invention (A), vinyl-vinyl acetate copolymer (EVA), ethylene-acrylic acid copolymer (EAA), ethylene-methacrylic acid copolymer (EMAA), the polar comonomers of ethylene-ethyl acrylate copolymer (EEA), ethylene ionomer type polar polymer content in described ethylene copolymer is about 5%-25 % by weight, and maleic anhydride content is about 0.1%-2% in ethene-maleic anhydride grafted polymer.Of the present invention aspect another, according to the ASTMD-1238(190 degree, 2.16 kilograms) test, the melt index (MI) with the ethylene copolymer of polar group described in the component (A) is 0.5-30g/10 minute.
Compare with polyethylene, vinyl-vinyl acetate copolymer (EVA) has been owing to introduced Vinyl Acetate Monomer in molecular chain, thereby reduced high-crystallinity.Vinyl acetate between to for plastic among the EVA (VA) content is in about 5%～40 % by weight.Common EVA has Taiwan to mould on the market
7350F, 7130F, 7140F etc., 8450 etc. of Japanese NUC company, and Dupont
3130,3190 etc.
Ethylene-acrylic acid copolymer (EAA), ethylene-methacrylic acid copolymer (EMAA), performance and the EVA of ethylene-ethyl acrylate copolymer (EEA) isopolarity ethylene copolymer have a lot of similarities.Common EAA has the Primacore (registered trademark) of Dow Chemical, as: 1410,3003,3002 etc.Common EMAA has the NUCREL (registered trademark) of du pont company, such as 3990,0910 etc.Common EEA has the Amplify (registered trademark) 101,103 of Dow Chemical etc.
Ionic polar ethylene polymkeric substance is the zinc of the hydrogen ion on the sour key in the resins such as EAA, a class ethene polymers that forms after sodium ion replaces.Zinc, sodium ion can form intermolecular crosslinked at normal temperatures, therefore, have greatly improved the physicals of polymkeric substance.Common Ionomer has the Surlyn (registered trademark) of Du Pont on the market, such as 1650,1610 etc.
The knot branch polymkeric substance of maleic anhydride-ethene is the ethene polymers with maleic anhydride monomer.The knot branch polymkeric substance of maleic anhydride-ethene can be by processing to prepare with the maleic anhydride as compatilizer (compatible) known in the art to ethylene copolymer (for example polyethylene).The method of Research of Grafting Malaic Anhydride Onto Polyethylene is a lot, mainly contains solution method, scorification, radiation method and solid phase method etc., and the most frequently used method is scorification, namely reacts extrusion molding.Common maleic anhydride polymer has the Bynel (registered trademark) of Du Pont on the market, and such as 30E753, the Admer (registered trademark) of 41E687 etc. and Mitsui company is such as AT1809, NF559 etc.
The component of polypropylene double-way stretched film of the present invention (B) can be and is selected from ethene and butene polymers, ethene and hexene oligomerization thing, the polyolefin elastomer of ethene and octene polymer, or the blend of described polymkeric substance.In one aspect of the invention, described component (B) is characterised in that, according to the DSC(dsc) test, its fusing point is less than 95 degree, preferably less than 90 degree.
In one aspect of the invention, described component (B) is metallocene quasi-polyethylene elastomerics.Described metallocene quasi-polyethylene is elastomeric to be characterised in that its comonomer distribution is even, comonomer distribution index CDBI〉55%, preferred CDBI〉65%, molecular weight distribution (Mw/Mn) only has an obvious melting peak during DSC test between 2-3.Mw/Mn can pass through GPC gel permeation chromatography technical measurement.CDBI is the index of comonomer distribution uniformity coefficient, and CDBI is larger, and comonomer distributes more even at main chain.The intensification fractionation extracting (TREF) of passing through of CDBI is measured, and its definition and testing method Wild wait the people in Journal of Polymer Science, Poly.Phys.Ed., Vol.20,441 (1982); US Patent No. 4,798,081, US5 has description in 008,204.
Preferably, be selected from ethene and butylene copolymer in the component of the functional layer of polypropylene double-way stretched film of the present invention (B), ethene and hexene copolymer, in the metallocene quasi-polyethylene of ethene and octene copolymer, in ethene and the octene copolymer octene content greater than 20 % by weight to being less than or equal between 40 % by weight, preferred octene content greater than 20 % by weight to being less than or equal between 30 % by weight, in ethene and the hexene copolymer hexene content greater than 15 % by weight to being less than or equal between 40 % by weight, preferred hexene content greater than 20 % by weight to being less than or equal between 30 % by weight, in ethene and the butylene copolymer butene content greater than 15 % by weight to being less than or equal between 40 % by weight, preferred butene content greater than 20 % by weight to being less than or equal between 40 % by weight, most preferably be greater than 20 % by weight to being less than or equal between 30 % by weight.Preferred, described metallocene quasi-polyethylene fusing point is lower than 95 degree.Preferred, described metallocene quasi-polyethylene, according to the ASTMD-1238(190 degree, 2.16 kilograms) test, its melt index (MI) is 0.5-30g/10 minute.
On the market there be the elastomerics of the common component that satisfies above-mentioned condition (B): the ENGAGE of Dow Chemical (registered trademark) LLDPE, such as EG 8200, EG8150; EG8770; The EXACT of Exxon Mobil Corporation (registered trademark) LLDPE is such as 0201,0203 etc.; The Tafmer of Mitsui chemistry (registered trademark) is such as A-4085, P-0480.
In one aspect, in the functional layer of polypropylene double-way stretched film of the present invention except said components (A) or component (B), or the blend of component (A) and component (B), optional, also contain component (C).In general, the amount of component (C) accounts for the functional layer gross weight and is lower than 40% weight, preferably is lower than 25%, more preferably less than 15%.Component (C) can help the processing characteristics of polypropylene double-way stretched film of the present invention, for example is beneficial to the adhesion phenomenon that occurs when overcoming rolling.
In one aspect of the invention, said components (C) can be higher than for fusing point the polyethylene that is selected from linear low density polyethylene (LLDPE), high density polyethylene(HDPE) (HDPE) or hp-ldpe (LDPE) of 100 degree.These polyethylene are according to the ASTMD-1238(190 degree, 2.16 kilograms) test melt index (MI) is 0.5-30 gram/10 minutes, fusing point is that about 95 degree-135 are spent.These common on market polyethylene comprise: Yanshan Petrochemical LDPE IF7B, the HDPE HTA108 of EXXON company, LLDPE 1002 etc.; The DOWLEX2045G of DOW Chemical, LDPE 640I etc.
In another aspect of the present invention, said components (C) can also be higher than for fusing point the metallocene quasi-polyethylene of 95 degree, and it is selected from ethene and butylene copolymer, ethene and hexene copolymer, ethene and octene copolymer, and the blend of described multipolymer.Nonvinylic co-monomer content is generally less than 20 % by weight in these multipolymers.This quasi-polyethylene comprises the AFFINITY1881 of DOW Chemical, and ELITE 5500; ELITE5815; The EVOLUE 1520 of Mitsui chemistry; EVOLUE 0540, EVOLUE2020 etc.
Aspect one of them, the longitudinal tensile strain rate of polypropylene double-way stretched film of the present invention and the ratio of cross direction elongation are less than 2, preferably less than 1.5 in the present invention.Longitudinal tensile strain rate and cross direction elongation refer to film on vertical or horizontal direction, stretch with certain trial speed and drawing force until the ratio of elongation and raw footage during fracture by stretching clamp.Longitudinal tensile strain rate and cross direction elongation can be tested by this area customary way and standard, for example test according to ASTM D-822.
In one aspect of the invention, the surface tension of the functional layer of film of the present invention is preferably between about 36-42 dynes per centimeter between about 36-48 dynes per centimeter.The functional layer surface (a non-side surface that contacts with basic unit) of polypropylene double-way stretched film of the present invention can be carried out surface treatment and be improved its surface tension.Common processing has corona treatment, flame treating or plasma treatment.
Polypropylene double-way stretched film of the present invention (BOPP film) is multilayered structure, and common is 3,4 or 5 layers, comprises one or more (for example two or three) basic unit and one or more (for example two or three) functional layer.The material of each basic unit or functional layer can be identical or different.
The basic unit of polypropylene double-way stretched film of the present invention can be one or more layers structure, for example two layers or three layers.When described basic unit was two layers or multilayer structure, the material of each basic unit was identical or different.Outermost basic unit is also referred to as the top layer.Polypropylene described above can be contained in described top layer, can also be mixed with polyethylene, for example high density polyethylene(HDPE) in addition.In one aspect of the invention, polypropylene and poly blend are contained in the top layer of described polypropylene double-way stretched film, and wherein polyethylene is high density polyethylene(HDPE), and polypropylene is homo-polypropylene or Co-polypropylene.
The functional layer of polypropylene double-way stretched film of the present invention can be one deck structure, also can be multilayered structure, and for example two layers or three layers, each layer component is identical or different.
The surface of polypropylene double-way stretched film of the present invention comprises that substrate surface (being a non-side surface that contacts with functional layer), functional layer surface (being a non-side surface that contacts with basic unit) can carry out surface treatment and improve its surface tension.For example, can after two-way stretch, process respectively or simultaneously and improve its surface tension.Common processing has corona treatment, flame treating or plasma treatment.In one aspect of the invention, surface treatment is carried out on the surface of the functional layer of film of the present invention, corona treatment for example, described film functional layer surface tension is preferably between about 36-42 dynes per centimeter between about 36-48 dynes per centimeter thus.In one aspect of the invention, can carry out corona treatment to the film substrate surface or to the functional layer surface, or simultaneously film substrate surface and functional layer surface be carried out corona treatment.
The thickness of polypropylene double-way stretched film of the present invention is about 10 microns-50 microns, and functional layer thickness is the 1-15 micron, is preferably the 3-10 micron.
The present invention also provides the method for preparing above-mentioned polypropylene double-way stretched film.
In one aspect, aforementioned polypropylene double-way stretched film of the present invention can pass through periosteum method (doublebubble is also referred to as two bubble method) bi-directional synchronization drawing process and is prepared.
The invention provides the method for the above-mentioned polypropylene double-way stretched film of preparation, comprising: (1) is with the polyolefine raw material, auxiliary material and or additive prepare by the composition of the basic unit of described polypropylene film and heat posted functional layer and mix, send into the forcing machine processing plasticizing; Through circular the first periosteum of annular machine capitiform, then cooling;
(2) the first periosteum is heated to draft temperature;
(3) the first periosteum is carried out cross directional stretch and longitudinal stretching, to predetermined stretch ratio and pre-determined thickness, form the second periosteum;
(4) cool off rapidly the second periosteum, then carry out heat setting type and process;
(5) surface tension adjustment is carried out on the surface of the second periosteum after the heat setting type;
(6) cooling;
(7) rolling and cutting.
In one aspect of the invention, wherein in the step (3) cross directional stretch and longitudinal stretching for carrying out synchronously.
In one aspect of the invention, the heat setting type of step (4) is the warming mill typing or steeps pipe by the 3rd and finalize the design.Preferably, described heat setting type is the warming mill typing.The heat setting temperature that uses among the present invention can be about 80 degree-120 degree.
In one aspect of the invention, the surface tension adjustment of step (5) can adopt the modes such as corona treatment, flame treating or plasma treatment to carry out surface tension adjustment.Surface tension adjustment can also be passed through the common methods such as method of chemical treatment, mechanical hacking method, coating.Preferably, the surface tension adjustment of step (5) is undertaken by corona treatment.The functional layer surface tension of the film that makes after the processing is preferably between about 36-42 dynes per centimeter between about 36-48 dynes per centimeter.
In one aspect of the invention, the longitudinal tensile strain rate of the film that makes and the ratio of cross direction elongation are less than about 2, preferably less than about 1.5.
The invention provides the polypropylene double-way stretched film for preparing according to the above-mentioned method for preparing polypropylene double-way stretched film.
The invention provides aforementioned polypropylene double-way stretched film of the present invention and various material are comprised the purposes that the paper heating is compound.
Aforementioned polypropylene double-way stretched film of the present invention can be used for various materials such as paper Zhang Jiare compound.The paper that paper can be paper blank or printed.This film also can be used for material heat posteds such as other plastics film and metallized films compound.This film also can be used for metal, pottery, and timber, the heat posted of the material surfaces such as glass is compound.This film also can be used for the BOPP basement membrane of aluminizing, and aluminium lamination can be by the vacuum aluminum-coated functional plane that is applied to.The thickness of aluminizing is about 10nm-100nm.
The invention provides the overlay film paper, it contains polypropylene double-way stretched film and the paper of the invention described above, wherein said polypropylene double-way stretched film comprises basic unit and thermal-adhering functional layer, described functional layer and paper are compound, described paper is selected from enamelled paper, offset paper, label paper, kraft paper, fluting board, sack kraft paper, glassine paper, ivory board and speciality paper.Wherein, described paper can be the paper of paper blank or printing.When described paper is the paper of printing, fit in the surface of the functional layer of described composite film material and paper printing printing ink.
Embodiment
The present invention's embodiment preferred with it combines when setting forth, and above description and the following example are to illustrate rather than limit the scope of the invention.
Material therefor details such as table one in following examples:
Table one: use raw material
The film of following examples 1-6 is produced at periosteum method bi-directional synchronization drawing process production line, and concrete technology is as follows:
According to each selected polyolefine raw material of prescription, auxiliary material and additive, mix and blend is sent into the forcing machine processing plasticizing through metering respectively; Through circular the first periosteum of annular machine capitiform; Cooling; Heat the first periosteum to suitable draft temperature, enter drawing zone through first pair of nip rolls, carry out synchronously cross directional stretch and longitudinal stretching the first periosteum, to predetermined stretch ratio and suitable thickness, form the second periosteum; Rapidly cooling; Enter the heat-treatment zone through second pair of nip rolls, carry out heat setting type by warming mill and process; The second periosteum after the corona treatment heat setting type; Cooling; Be wound into large film parent roll; After slaking in 48 hours, cut into the finished film that needs width.
Embodiment 1:
Produce 20 microns BOPP heat posted protective membranes at 5 layers of co-extrusion two bubble method two-way stretch equipment, its structure sees the following form.
Complete processing and parameter
The functional layer of the polypropylene double-way stretched film of embodiment 1 is measured according to dsc (DSC), and the ratio that the melting peak areas that fusing point is lower than 90 degree on its DSC curve account for the DSC curve total area is about 90%.
Embodiment 2:
Produce 20 microns BOPP heat posted protective membrane at 5 layers of co-extrusion two bubble method (Double Bubble Process) two-way stretch equipment, its structure sees the following form.
Complete processing and parameter
The functional layer of the polypropylene double-way stretched film of embodiment 2 is measured according to dsc (DSC), and the ratio that the melting peak areas that fusing point is lower than 90 degree on its DSC curve account for the DSC curve total area is about 75%.
Embodiment 3:
Produce BOPP heat posted protective membrane at 5 layers of co-extrusion two bubble method two-way stretch equipment, its structure sees the following form.
Complete processing and parameter
The functional layer of the polypropylene double-way stretched film of embodiment 3 is measured according to dsc (DSC), and the ratio that the melting peak areas that fusing point is lower than 90 degree on its DSC curve account for the DSC curve total area is about 72%.
Embodiment 4:
Produce BOPP heat posted protective membrane at 5 layers of co-extrusion two bubble method two-way stretch equipment, its structure sees the following form.
Complete processing and parameter
The functional layer of the polypropylene double-way stretched film of embodiment 3 is measured according to dsc (DSC), and the ratio that the melting peak areas that fusing point is lower than 90 degree on its DSC curve account for the DSC curve total area is about 48%.
Embodiment 5:
Produce BOPP heat posted protective membrane at 5 layers of co-extrusion two bubble method (double bubble) two-way stretch equipment, its structure sees the following form.
Complete processing and parameter
The functional layer of the polypropylene double-way stretched film of embodiment 5 is measured according to dsc (DSC), and the ratio that the melting peak areas that fusing point is lower than 90 degree on its DSC curve account for the DSC curve total area is about 82%.
Embodiment 6:
Produce BOPP heat posted protective membrane at 5 layers of co-extrusion two bubble method (double bubble) two-way stretch equipment, its structure sees the following form.
Complete processing and parameter
The functional layer of the polypropylene double-way stretched film of embodiment 6 is measured according to dsc (DSC), and the ratio that the melting peak areas that fusing point is lower than 90 degree on its DSC curve account for the DSC curve total area is about 53%.
Embodiment 7:
Produce BOPP heat posted protective membrane at 7 layers of co-extrusion two bubble method (double bubble) two-way stretch equipment, its structure sees the following form.
Complete processing and parameter
The functional layer of the polypropylene double-way stretched film of embodiment 7 is measured according to dsc (DSC), and the ratio that the melting peak areas that fusing point is lower than 90 degree on its DSC curve account for the DSC curve total area is about 82%.
The DSC(dsc) testing method is as follows:
Dsc measurement carries out at Perkin Elmer System 7Thermal Analysis System.Testing method is: 1) institute's specimen is heated to 180 degree, then the weighing apparatus temperature is 5 minutes; 2) sample is cooled to 20 degree with 10 degrees/mins speed; 3) with 10 degrees/mins speed sample is heated to 180 degree.The endothermic curve in the 3rd step is the melt temperature curve.
The result shows, although draft temperature has reached more than 140 degree in the production technique of above-described embodiment, much larger than the material melting point of heat posted face, film of the present invention has adopted unique explained hereafter, film is in vacant state in the whole drawing process, therefore stretches and can carry out smoothly.And in test is produced, prescription according to said film, adopt the flat embrane method production technique of traditional BOPP, in process of production, the BOPP film when longitudinal stretching will with the warming mill Surface Contact, and the PP draft temperature is greater than 120 degree, causes film when stretching and longitudinal stretching roller surface produces adhesion, and can't produce.
Combined strength bination and other the performance test results of BOPP film of the present invention and contrast film and paper heat posted see Table two.Contrast film 8 is to be coated with the structure that one deck VA content is 18% vinyl-vinyl acetate copolymer (EVA) by extrusion coated with traditional technology again on common BOPP film surface, and concrete structure is BOPP(15 μ)/glue/EVA(6 μ):
Table two: film performance
Can find out one-time formed polypropylene double-way stretched film of the present invention and traditional pass through extrusion coated twice moulding pre-coating film relatively from table two, and the applying fastness of paper do not have difference substantially, in addition more excellent.And film of the present invention has the less characteristics of vertical lateral performance difference.
Polypropylene double-way stretched film is flat embrane method preparation basically in the technology now, wherein adopts the technique of step drawing, therefore, vertical and horizontal performance has larger difference, as, elongation is much larger than cross direction elongation longitudinally, and vertical and horizontal elongation is than greater than 2.0.And the present invention adopts the periosteum method to produce polypropylene double-way stretched film, and its vertical and horizontal performance is very approaching, and vertical and horizontal elongation ratio is generally less than 2, even lower, for example is 1.5.
Unless otherwise noted, practice of the present invention will be used the routine techniques of organic chemistry, polymer chemistry etc., obviously except the special description of institute in above-mentioned explanation and embodiment, can also other mode realize the present invention.Other aspect within the scope of the present invention will be apparent to those skilled in the art in the invention with improvement.According to instruction of the present invention, many changes and variation are feasible, so it within the scope of the present invention.
All patents mentioned in this article, patent application and technical paper all are attached to this paper accordingly by reference.
As without special expression, the unit " degree " of the temperature that occurs herein refers to degree centigrade, namely ℃.
Claims (10)
1. polypropylene double-way stretched film, it has basic unit and the heat posted functional layer of coextru-lamination, and wherein said functional layer comprises the blend of component (A) or component (B) or component (A) and component (B), wherein:
Component (A) is the ethylene copolymer with polar group, it is selected from vinyl-vinyl acetate copolymer (EVA), ethylene-acrylic acid copolymer (EAA), ethylene-methacrylic acid copolymer (EMAA), ethylene-ethyl acrylate copolymer (EEA), ethylene ionomer type polar polymer, ethene-maleic anhydride grafted polymer and its blend, be preferably EVA or ethene-maleic anhydride grafted polymer, described component (A) is characterised in that, test according to dsc (DSC), its fusing point is lower than 95 degree, preferably is lower than 90 degree;
Component (B) is selected from ethene and butylene copolymer, ethene and hexene copolymer, the blend of ethene and octene copolymer and described multipolymer, and described component (B) is characterised in that, test according to dsc (DSC), its fusing point is lower than 95 degree, preferably is lower than 90 degree
Wherein, the longitudinal tensile strain rate of described polypropylene double-way stretched film and the ratio of cross direction elongation are less than 2, and preferably less than 1.5, and described film functional layer surface tension is preferably between the 36-42 dynes per centimeter between the 36-48 dynes per centimeter.
2. the polypropylene double-way stretched film of preparation claim 1, described functional layer is measured according to dsc (DSC), and fusing point is lower than ratio that the peak area of the parts of 90 degree accounts for the DSC curve total area greater than 30% on its DSC curve, is preferably greater than 50%.
3. claim 1 or 2 polypropylene double-way stretched film, wherein in the ethylene copolymer with polar group in the component (A), vinyl-vinyl acetate copolymer (EVA), ethylene-acrylic acid copolymer (EAA), ethylene-methacrylic acid copolymer (EMAA), ethylene-ethyl acrylate copolymer (EEA), the polar monomer of ethylene ionomer type polar polymer content in described ethylene copolymer is the 5%-25 % by weight, maleic anhydride content is 0.1%-2% in ethene-maleic anhydride grafted polymer, preferably, according to the ASTMD-1238(190 degree, 2.16 kilogram) test, the melt index (MI) with the ethylene copolymer of polar group described in the component (A) is 0.5-30g/10 minute.
4. each polypropylene double-way stretched film among the claim 1-3, wherein multipolymer is the metallocene quasi-polyethylene described in the component (B), in ethene and the octene copolymer octene content greater than 20 % by weight to being less than or equal between 40 % by weight, be preferably more than 20 % by weight to being less than or equal between 30 % by weight, in ethene and the hexene copolymer hexene content greater than 15 % by weight to being less than or equal between 40 % by weight, be preferably more than 20 % by weight to being less than or equal between 30 % by weight, in ethene and the butylene copolymer butene content greater than 15 % by weight to being less than or equal between 40 % by weight, preferred butene content greater than 20 % by weight to being less than or equal between 40 % by weight, most preferably be greater than 20 % by weight to being less than or equal between 30 % by weight
Preferably, according to the ASTMD-1238(190 degree, 2.16 kilograms) test, its melt index (MI) is 0.5-30g/10 minute.
5. each polypropylene double-way stretched film among the claim 1-4, its functional layer also contains component (C), and component (C) is:
(1) be selected from the polyethylene of linear low density polyethylene (LLDPE), high density polyethylene(HDPE) (HDPE) and hp-ldpe (LDPE), its fusing point is greater than 100 degree,
Or
(2) metallocene quasi-polyethylene, it is selected from ethene and butylene copolymer, ethene and hexene copolymer, and ethene and octene copolymer, and the blend of described multipolymer, wherein said metallocene quasi-polyethylene fusing point are higher than 95 degree,
Preferably, described component (C) accounts for the functional layer gross weight and is lower than 40% weight, preferably is lower than 25% weight, more preferably less than 15% weight.
6. each polypropylene double-way stretched film among the claim 1-5, described basic unit and tack coat respectively are one deck, two layers or three-decker, wherein the component of each basic unit or each functional layer is identical or different.
7. each polypropylene double-way stretched film among the claim 1-6 is characterized in that described overall film thickness is 10 microns-50 microns, and the thickness of described functional layer is the 1-15 micron, is preferably the 3-10 micron.
8. overlay film paper, it contains among the claim 1-7 each polypropylene double-way stretched film and paper, wherein said polypropylene double-way stretched film comprises basic unit and heat posted functional layer, described functional layer and paper are compound, described paper is selected from enamelled paper, offset paper, label paper, kraft paper, fluting board, sack kraft paper, glassine paper, ivory board and speciality paper.
9. preparation method who prepares each polypropylene film among the claim 1-7 comprises:
(1) with the polyolefine raw material, auxiliary material and/or additive are prepared by the composition of the basic unit of described polypropylene film and heat posted functional layer and are mixed, and send into the forcing machine processing plasticizing; Through circular the first periosteum of annular machine capitiform, then cooling;
(2) the first periosteum is heated to draft temperature;
(3) the first periosteum is carried out synchronous horizontal and stretch and longitudinal stretching, to predetermined stretch ratio and pre-determined thickness, form the second periosteum;
(4) cool off rapidly the second periosteum, then carry out heat setting type and process;
(5) surface tension adjustment is carried out on the surface of the second periosteum after the heat setting type, be preferably and pass through corona treatment;
(6) cooling;
(7) rolling and cutting.
10. the method for claim 9, wherein, the heat setting type of step (4) is warming mill typing or by the 3rd bubble pipe typing, preferred, described heat setting type is the warming mill typing.
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