CN103059763B - 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 high transparency, nontoxic, moistureproof, ventilation property is low, deflection advantages of higher, is widely used in packaging and the lamination compound of the products such as food, medicine, daily light industry, cigarette.BOPP film wherein a kind of purposes fits in paper surface, and as books, packing carton etc., play a part moistureproof and 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 is generally made up of homo-polypropylene, also can mix some functional agents, as white master batch and pearlescent additive etc.Outside basic unit is generally homo-polypropylene and additive or delustring material and forms.Functional layer is generally used for heat posted compound.
Polypropylene double-way stretched film is modal is produce by flat embrane method two-way stretch (tenter framebi-orientation) technique, and its production technique forms primarily of following operation: 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-preheating-cross directional stretch-heat setting type-cooling-corona treatment-rolling again-cut-put in storage.
BOPP important application in packaging is paper overlay film, namely by professional equipment for coating film by paper printing products together with BOPP Film laminated, form the product of paper unification, this technology is called film coating technique (Film lamination).Through the paper printing matter of 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, some visual defects even in printing process can be made up to a great extent, therefore, not only extend work-ing life, the aesthetic property of product also substantially increases.Recombining process is in the market divided into solvent-borne type to be namely coated with technology, water-soluble i.e. painting technology and precoating technology.
Namely solvent-borne type is coated with technology is utilize special i.e. coat film equipment to be coated on BOPP film by the solvent-borne type blent through benzene solvent and gluing, and drying and heating, pressurization, with printing compound.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.Namely water-based is coated with technology is namely be coated with on the basis of technology at former solvent-borne type, replaces organic solvent glue with nontoxic water-base cement (i.e. water-based acrylic acid ester sizing agent), thus solves the pollution problem that namely solvent-borne type is coated with technology existence.
Although namely water-based is coated with technique and solves the benzene pollution problem that namely solvent-borne type be coated with, but there is the pollution problem after needing the cleaning of large water gaging and discharge cleaning sullage in it, it not still optimal environment-friendly type overlay film solution, simultaneously, namely water-based is coated with technique and there is the lower problem of the compound fastness of BOPP and paper, easily occurs film and paper delamination in use procedure.
Namely above-mentioned two kinds of BOPP are coated with technology and there is the inefficient defect of overlay film.Owing to all needing through the link such as gluing, oven dry in coating process, therefore overlay film speed is restricted, and is only 15-30 m/min, the post-press finishing demand after far can not meeting high speed printing.Namely the laminating fastness that the defect being coated with technique also comprises BOPP and paper is low, and recombination process needs to use environmentally harmful tackiness agent and solvent, and meanwhile, in glue dries process, evaporating solvent can cause larger energy consumption.
Disclose one in CN2741769Y and be coated with one deck ethylene-vinyl acetate copolymer (EVA) raw material at BOPP film surface by extruding, and then heat the technique of compound with paper.This film with EVA is pre-coating film.Its production process is, pre-coating film manufactory will meet the BOPP thin-film material of particular technology requirement, is coated with one deck EVA raw material by extrusion coated (extrusion coating) on BOPP surface.Printing packaging enterprise to during paper printing products coating process without the need to doing any coating process to film again, only need by special laminating machine heating and pressurizing.The distinctive production technique of pre-coating film and coating process make its can high, the cohesive strength of high speed overlay film (60-100 m/min), compound film quality far above being namely coated with the advantages such as technique is high, overlay film post-treatment performance is good.But pre-coating film needs secondary to apply the secondary processing technique of one deck EVA on the BOPP film produced, and EVA price comparison is expensive.
Disclose a kind of paper-plastic stick polypropylene double-way stretched film in CN100566994C, this film has top layer, sandwich layer and can with paper add thermal-adhering functional layer composition and formed by stretch processes time processing.This technology overcomes existing i.e. painting technology to be needed gluing and causes potential environmental influence and can cause the shortcomings such as larger energy consumption because of evaporating solvent in glue dries process, and the film once shaped of this technology, does not need to need secondary to apply the secondary processing technique of one deck EVA as pre-coating film on the BOPP film produced.But this technology is because be subject to the restriction of the film stretching adhesion in the course of processing, EVA can not be used to do functional layer, and the polyolefine that fusing point is higher can only be used, if co-monomer content is at the ethylene-octene copolymer of 5%-20% and the ethylene-butene copolymer of co-monomer content between 10%-30%.These multipolymers are because comonomer is less, and fusing point is all higher than 95 degree, and therefore, drawing process does not have adhesion.But, defect is that temperature when adding thermal-adhering is far above existing EVA pre-coating film, overlay film speed not only can be caused low, and the stripping fastness after its overlay film is far below EVA pre-coating film, and the composite membrane that therefore this technology is produced can only reach and be the overlay film speed and laminating fastness that film is suitable.
Therefore, industry member needs simple, the one-time formed BOPP film of a kind of technique, and this film has with paper laminating fastness high, and the feature that overlay film efficiency is high, can also overcome the adhesion of functional layer and processing units in 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 (i.e. hot melt adhesive) of coextru-lamination.Polypropylene double-way stretched film of the present invention can be used for and the material heat posted compounds such as paper.Polypropylene double-way stretched film of the present invention has high transparency, high-stiffness, and with the excellent hot composite performance of the materials such as paper, its overlay film speed is suitable with existing EVA pre-coating film with overlay film intensity, and time processing drawing and forming, overcomes the shortcoming that 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, ethylene-maleic acid graftomer and its blend, the feature of described component (A) is, test according to dsc (DSC), its fusing point lower than about 95 degree, preferably 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, the feature of described component (B) is, tests according to dsc (DSC), its fusing point lower than about 95 degree, preferably lower than about 90 degree.
In one aspect of the invention, the longitudinal tensile strain rate of above-mentioned polypropylene double-way stretched film is less than about 2 with the ratio of cross direction elongation, preferably be less than about 1.5, and described film functional layer surface tension is between about 36-48 dynes per centimeter, is preferably between about 36-42 dynes per centimeter.
Of the present invention in another, above-mentioned polypropylene double-way stretched film is by periosteum method (DoubleBubble Process, 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 on its DSC curve, fusing point accounts for the DSC curve total area lower than the peak area of the part of 90 degree is greater than about 30%, is preferably greater than about 50%.
Of the present invention in another, be vinyl-vinyl acetate copolymer (EVA) with the ethylene copolymer of polar group described in component (A).
Of the present invention in another, be ethylene-maleic acid graftomer with the ethylene copolymer of polar group described in component (A).
In one aspect, described in the component (A) of polypropylene double-way stretched film of the present invention with the ethylene copolymer of polar group (in the present invention, sometimes also referred to as the ethene polymers with polar group) feature be, wherein in ethylene-maleic acid graftomer, maleic anhydride content is about 0.1%-2%, wherein vinyl-vinyl acetate copolymer (EVA), ethylene-acrylic acid copolymer (EAA), ethylene-methacrylic acid copolymer (EMAA), ethylene-ethyl acrylate copolymer (EEA), it is about 5%-25% that polarity in ethylene ionomer type polar polymer gathers monomer weight content in described polar ethylene copolymer.
Of the present invention in another, according to ASTMD-1238(190 degree, 2.16 kilograms) test, the melt index (MI) with the ethylene copolymer of polar group described in component (A) is 0.5-30g/10 minute.
In one aspect, in polypropylene double-way stretched film of the present invention, the polyolefin elastomer of component (B) is 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, wherein in ethene and octene copolymer, octene content is being greater than 20 % by weight to being less than or equal between 40 % by weight, be preferably greater than 20 % by weight to being less than or equal between 30 % by weight, in ethene and hexene copolymer, ahexene content is being greater than 15 % by weight to being less than or equal between 40 % by weight, be preferably greater than 20 % by weight to being less than or equal between 30 % by weight, or butene content is being greater than 15 % by weight to being less than or equal between 40 % by weight in ethene and butylene copolymer, preferred butene content is being greater than 20 % by weight to being less than or equal between 40 % by weight, most preferably be and be greater than 20 % by weight to being less than or equal between 30 % by weight.Of the present invention in another, described metallocene quasi-polyethylene, according to 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 is also containing 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 functional layer gross weight lower than about 40% weight, preferably 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.Described basic unit can containing the thermoplastic polymer with film-forming properties.In general, described basic unit is made up of the material based on polypropylene.The polyolefine of basic unit of the present invention film-forming polymer can be used as and comprise alfon, Co-polypropylene or its blend composition, typically be isotaxy homopolymer, atactic polypropylene(APP), syndiotactic polypropylene, have the polypropylene blend of the atactic copolymerized polypropene of a small amount of ethene or higher-alkene and ethylene copolymer-modified isotactic polyprophlene.Other component can be added if the additives such as petroleum resin are to change such as deflection, the performances such as frictional coefficient in basic unit.Although base material is made up of homo-polypropylene (Ho-PP) in most cases, base material also can be made up of the blend of binary or ternary polymerized polypropylene (Co-PP) or itself and homo-polypropylene.
In one aspect of the invention, according to ASTMD-1238(230 degree, 2.16 kilograms) test, the melt index (MI) of described base material is about 0.5-15g/10 minute.
Base material material also can add the polyethylene being 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
3or higher (such as about 0.952g/cm
3to about 0.968g/cm
3) density, about 266 ℉ to the fusing point of about 299 ℉ (about 130 DEG C to about 148 DEG C), and are less than the melting index (measuring according to ASTM D1238) of 1 to 50 gram/10 minutes (such as 1 to 50 gram/10 minutes).
LDPE is homopolymer polymer, generally has at 0.912g/cm
3to 0.94g/cm
3(such as 0.915g/cm
3to 0.928g/cm
3) the density of scope, and the melting index of 0.2 to 50 gram/10 minutes (such as 1 to 10 gram/10 minutes) (measuring according to ASTM D1238).LDPE can use radical initiator to produce in high-pressure process.The LDPE be under high pressure polymerized is sometimes referred to as high-pressure polyethylene.
LLDPE can be divided into ethene and butylene copolymer, ethene and hexene copolymer and ethene and octene copolymer, generally there is the melting index (measuring according to ASTM D1238) being less than 1 to 50 gram/10 minutes (such as 1 to 10 gram/10 minutes), and 0.910 to 0.940g/cm
3, preferably 0.915 to 0.928g/cm
3the density of scope.
The industrial homo-polypropylene (Ho-PP) conventional for two-way stretch BOPP film has: the T38F of Lanzhou Petrochemical and Daqing petrochemical; The T36F of Dalian petrochemical industry.This kind of homo-polypropylene according to ASTMD-1238(230 degree, 2.16 kilograms) test melt index (MI) can be about 0.5-15 gram/10 minutes, fusing point can be about 155 degree-168 spend between.
The additive of about 0.01%-5% can be added with master batch form in base material.Some typical additives have, antiblocking agent, slipping agent, static inhibitor, nucleator etc.Base material also can comprise on a small quantity, the petroleum resin of such as 1%-15%, and petroleum resin can be low-molecular-weight, to improve the deflection of film and to lower draft temperature.Petroleum resin can be through hydrotreated.Also can add delustring masterbatch in base material and carry out production delustring BOPP film.Also pearly-lustre masterbatch can be added to produce pearly-lustre BOPP film in base material.Base material homo-polypropylene (Ho-PP) mainly provide deflection, water vapor rejection, transparency and processibility.In base material, homo-polypropylene (Ho-PP) can account for the thickness of whole film is about 50%-95%.
Outermost basic unit is also referred to as top layer.Polypropylene described above can be contained in described top layer, polyethylene can also be mixed with in addition, it is selected from the polyethylene of high density polyethylene(HDPE) (HDPE), Low Density Polyethylene (LDPE) and LLDPE (LLDPE), such as, 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 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) be with polar group ethylene copolymer (in the present invention, sometimes 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, ethylene-maleic acid graftomer and its blend, the feature of described component (A) is, test according to dsc (DSC), its fusing point is lower than about 95 degree, preferably 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, the feature of described component (B) is, test according to dsc (DSC), its fusing point lower than about 95 degree, preferably lower than about 90 degree
Wherein, the longitudinal tensile strain rate of described polypropylene double-way stretched film is less than about 2 with the ratio of cross direction elongation, is preferably less than about 1.5, and described film functional layer surface tension is between about 36-48 dynes per centimeter, is preferably between about 36-42 dynes per centimeter.
In one aspect, be characterised in that with the polyvinyl of polar group described in the component (A) of polypropylene double-way stretched film of the present invention, vinyl-vinyl acetate copolymer (EVA), ethylene-acrylic acid copolymer (EAA), ethylene-methacrylic acid copolymer (EMAA), polar comonomers content in described ethylene copolymer of ethylene-ethyl acrylate copolymer (EEA), ethylene ionomer type polar polymer is about 5%-25 % by weight, and in ethylene-maleic acid graftomer, maleic anhydride content is about 0.1%-2%.Of the present invention in another, according to ASTMD-1238(190 degree, 2.16 kilograms) test, the melt index (MI) with the ethylene copolymer of polar group described in component (A) is 0.5-30g/10 minute.
Compared with polyethylene, vinyl-vinyl acetate copolymer (EVA) owing to introducing Vinyl Acetate Monomer in molecular chain, thus reduces high-crystallinity.In EVA, vinyl acetate between to for plastic (VA) content is about 5% ~ 40 % by weight.EVA common on market has Taiwan to mould
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 similarity.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, as 3990, and 0910 etc.Common EEA has the Amplify (registered trademark) 101,103 etc. of Dow Chemical.
Ionic polar ethylene polymer is the hydrogen ion zinc on key sour in the resins such as EAA, the class ethene polymers formed after sodium ion replaces.Zinc, sodium ion can be formed intermolecular crosslinked at normal temperatures, therefore, substantially increases the physicals of polymkeric substance.Ionomer common on market has the Surlyn (registered trademark) of Du Pont, as 1650, and 1610 etc.
The knot branch polymkeric substance of maleic anhydride/vinyl is the ethene polymers with maleic anhydride monomer.The knot branch polymkeric substance of maleic anhydride/vinyl can by preparing ethylene copolymer (such as polyethylene) the maleic anhydride process as compatilizer (compatible) known in the art.The method of Research of Grafting Malaic Anhydride Onto Polyethylene is a lot, and mainly contain solution method, scorification, radiation method and solid phase method etc., the most frequently used method is scorification, i.e. reactive extrursion method.Maleic anhydride polymer common on market has the Bynel (registered trademark) of Du Pont, if the Admer (registered trademark) of 30E753,41E687 etc. and Mitsui company is as AT1809, NF559 etc.
The component (B) of polypropylene double-way stretched film of the present invention 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, the feature of described component (B) is, according to DSC(dsc) test, its fusing point is less than 95 degree, is 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 is characterised in that its comonomer distribution is even, comonomer distribution index CDBI>55%, preferred CDBI>65%, molecular weight distribution (Mw/Mn), between 2-3, only has an obvious melting peak during DSC test.Mw/Mn is by GPC gel permeation chromatography technical measurement.CDBI is the index of comonomer distribution uniformity coefficient, and CDBI is larger, and comonomer distributes more even on main chain.CDBI is measured by intensification fractionation extracting (TREF), and its definition and testing method Wild, wait people at Journal of Polymer Science, Poly.Phys.Ed., Vol.20,441 (1982); US Patent No. 4,798,081, US5,008, there is description in 204.
Preferably, ethene and butylene copolymer is selected from the component (B) of the functional layer of polypropylene double-way stretched film of the present invention, ethene and hexene copolymer, in the metallocene quasi-polyethylene of ethene and octene copolymer, in ethene and octene copolymer, octene content is being greater than 20 % by weight to being less than or equal between 40 % by weight, preferred octene content is being greater than 20 % by weight to being less than or equal between 30 % by weight, in ethene and hexene copolymer, ahexene content is being greater than 15 % by weight to being less than or equal between 40 % by weight, preferred ahexene content is being greater than 20 % by weight to being less than or equal between 30 % by weight, in ethene and butylene copolymer, butene content is being greater than 15 % by weight to being less than or equal between 40 % by weight, preferred butene content is being greater than 20 % by weight to being less than or equal between 40 % by weight, most preferably be and 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 ASTMD-1238(190 degree, 2.16 kilograms) test, its melt index (MI) is 0.5-30g/10 minute.
The elastomerics of the component (B) meeting above-mentioned condition common on market has: ENGAGE (registered trademark) LLDPE of Dow Chemical, as EG 8200, EG8150; EG8770; EXACT (registered trademark) LLDPE of Exxon Mobil Corporation, as 0201,0203 etc.; The Tafmer (registered trademark) of Mitsui chemistry is as A-4085, P-0480.
In one aspect, except said components (A) or component (B) in the functional layer of polypropylene double-way stretched film of the present invention, or the blend of component (A) and component (B), optional, also containing component (C).In general, the amount of component (C) accounts for functional layer gross weight lower than 40% weight, preferably lower than 25%, more preferably less than 15%.Component (C) can contribute to the processing characteristics of polypropylene double-way stretched film of the present invention, such as, be beneficial to the adhesion phenomenon occurred when overcoming rolling.
In one aspect of the invention, said components (C) can for fusing point be higher than the polyethylene being selected from linear low density polyethylene (LLDPE), high density polyethylene(HDPE) (HDPE) or hp-ldpe (LDPE) of 100 degree.These polyethylene according to ASTMD-1238(190 degree, 2.16 kilograms) test melt index (MI) be 0.5-30 gram/10 minutes, fusing point be about 95 degree-135 spend.These polyethylene common on market comprise: the HDPE HTA108 of Yanshan Petrochemical LDPE IF7B, 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 fusing point higher than 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.In these multipolymers, nonvinylic co-monomer content is generally less than 20 % by weight.This quasi-polyethylene comprises the AFFINITY1881 of DOW Chemical, ELITE 5500; ELITE5815; The EVOLUE 1520 of Mitsui chemistry; EVOLUE 0540, EVOLUE2020 etc.
In the present invention in 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, are preferably less than 1.5.Longitudinal tensile strain rate and cross direction elongation refer to that film is on vertical or horizontal direction, stretched with certain trial speed and drawing force by stretching clamp until fracture time elongation and the ratio of raw footage.Longitudinal tensile strain rate and cross direction elongation are tested by this area customary way and standard, such as, 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, between about 36-48 dynes per centimeter, is preferably between about 36-42 dynes per centimeter.The functional layer surface (the non-side surface contacted 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 process 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 (such as two or three) basic unit and one or more (such as two or three) functional layer.The material of each basic unit or functional layer may be the same or different.
The basic unit of polypropylene double-way stretched film of the present invention can be one or more layers structure, such as two layers or three layers.When described basic unit is two layers or multilayer structure, the material of each basic unit is identical or different.Outermost basic unit is also referred to as top layer.Polypropylene described above can be contained in described top layer, can also be mixed with polyethylene in addition, such as 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 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 a Rotating fields, also can be multilayered structure, and such as 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 substrate surface (i.e. the non-side surface contacted with functional layer), functional layer surface (i.e. the non-side surface contacted with basic unit) can carry out surface treatment and improve its surface tension.Such as, after two-way stretch, process can be carried out respectively or simultaneously and improves its surface tension.Common process has corona treatment, flame treating or plasma treatment.In one aspect of the invention, carry out surface treatment, such as corona treatment to the surface of the functional layer of film of the present invention, described film functional layer surface tension is between about 36-48 dynes per centimeter thus, is preferably between about 36-42 dynes per centimeter.In one aspect of the invention, corona treatment can be carried out to film substrate surface or to functional layer surface, or corona treatment be carried out to film substrate surface and functional layer surface simultaneously.
The thickness of polypropylene double-way stretched film of the present invention is about 10 microns-50 microns, and functional layer thickness is 1-15 micron, is preferably 3-10 micron.
Present invention also offers the method 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, also referred to as two bubble method) bi-directional synchronization drawing process and is prepared.
The invention provides the method preparing above-mentioned polypropylene double-way stretched film, comprising: (1) is by polyolefinic raw materials, auxiliary material and or additive undertaken preparing and mixing by the basic unit of described polypropylene film and the composition of heat posted functional layer, send into forcing machine processing plasticizing; Through circular first periosteum of annular machine capitiform, then cool;
(2) the first periosteum is heated to draft temperature;
(3) cross directional stretch and longitudinal stretching are carried out to the first periosteum, to predetermined stretch ratio and pre-determined thickness, form the second periosteum;
(4) cool the second periosteum rapidly, then carry out heat setting type process;
(5) surface tension adjustment is carried out to the surface of the second periosteum after heat setting type;
(6) cool;
(7) rolling and cutting.
In one aspect of the invention, wherein in step (3) cross directional stretch and longitudinal stretching for synchronously to carry out.
In one aspect of the invention, the heat setting type of step (4) is warming mill sizing or is shaped by the 3rd bubble pipe.Preferably, described heat setting type is warming mill sizing.The heat setting temperature used in the present invention can be about 80 degree of-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 pass 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 film obtained after process, between about 36-48 dynes per centimeter, is preferably between about 36-42 dynes per centimeter.
In one aspect of the invention, the obtained longitudinal tensile strain rate of film is less than about 2 with the ratio of cross direction elongation, is preferably less than about 1.5.
The invention provides the polypropylene double-way stretched film prepared according to the above-mentioned method preparing polypropylene double-way stretched film.
The invention provides and aforementioned polypropylene double-way stretched film of the present invention and various material are comprised the purposes that paper heats compound.
Aforementioned polypropylene double-way stretched film of the present invention can be used for and 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 and other material such as plastics film and metallized film heat posted compound.This film also can be used for metal, pottery, timber, the heat posted compound of the material surfaces such as glass.This film also can be used for BOPP basement membrane of aluminizing, and aluminium lamination is applied to functional plane by vacuum aluminum-coated.Thickness of aluminizing is about 10nm-100nm.
The invention provides 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 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, the functional layer of described composite film material and the surface laminating of paper printing ink.
Embodiment
When the present invention combines elaboration with its preferred embodiment, above description and the following example are used to illustrate instead of limit the scope of the invention.
In following examples, material therefor details are as table one:
Table one: use raw material
The film of following examples 1-6 is produced on periosteum method bi-directional synchronization drawing process production line, and concrete technology is as follows:
According to formula each polyolefinic raw materials of select, auxiliary material and additive, respectively mix and blend, through metering feeding forcing machine processing plasticizing; Through circular first periosteum of annular machine capitiform; Cooling; Heat the first periosteum to suitable draft temperature, enter drawing zone through first pair of nip rolls, synchronously carry out cross directional stretch and longitudinal stretching first periosteum, to predetermined stretch ratio and suitable thickness, form the second periosteum; Rapid cooling; Enter heat-treatment zone through second pair of nip rolls, carry out heat setting type process by warming mill; The second periosteum after corona treatment heat setting type; Cooling; Be wound into large film parent roll; The finished film needing width is cut into after slaking in 48 hours.
embodiment 1:
5 layers of co-extrusion two bubble method two-way stretch equipment produce 20 microns of BOPP heat posted protective membranes, and 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 on its DSC curve, fusing point accounts for the DSC curve total area lower than the melting peak area of 90 degree is about 90%.
embodiment 2:
5 layers of co-extrusion two bubble method (Double Bubble Process) two-way stretch equipment is produced the BOPP heat posted protective membrane of 20 microns, and 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 on its DSC curve, fusing point accounts for the DSC curve total area lower than the melting peak area of 90 degree is about 75%.
Embodiment 3:
5 layers of co-extrusion two bubble method two-way stretch equipment produce BOPP heat posted protective membrane, and 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 on its DSC curve, fusing point accounts for the DSC curve total area lower than the melting peak area of 90 degree is about 72%.
Embodiment 4:
5 layers of co-extrusion two bubble method two-way stretch equipment produce BOPP heat posted protective membrane, and 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 on its DSC curve, fusing point accounts for the DSC curve total area lower than the melting peak area of 90 degree is about 48%.
Embodiment 5:
5 layers of co-extrusion two bubble method (double bubble) two-way stretch equipment produces BOPP heat posted protective membrane, and 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 on its DSC curve, fusing point accounts for the DSC curve total area lower than the melting peak area of 90 degree is about 82%.
Embodiment 6:
5 layers of co-extrusion two bubble method (double bubble) two-way stretch equipment produces BOPP heat posted protective membrane, and 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 on its DSC curve, fusing point accounts for the DSC curve total area lower than the melting peak area of 90 degree is about 53%.
Embodiment 7:
7 layers of co-extrusion two bubble method (double bubble) two-way stretch equipment produces BOPP heat posted protective membrane, and 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 on its DSC curve, fusing point accounts for the DSC curve total area lower than the melting peak area of 90 degree is about 82%.
DSC(dsc) testing method is as follows:
Dsc measurement carries out on Perkin Elmer System 7Thermal Analysis System.Testing method by: 1) be heated to 180 degree testing sample, then weighing apparatus temperature 5 minutes; 2) sample is cooled to 20 degree with the speed of 10 degrees/min; 3) with the speed of 10 degrees/min, sample is heated to 180 degree.The endothermic curve of the 3rd step is melt temperature curve.
Result shows, although draft temperature reaches more than 140 degree in the production technique of above-described embodiment, much larger than the material melting point in heat posted face, film of the present invention have employed unique explained hereafter, in whole drawing process, film is in vacant state, therefore stretches and can carry out smoothly.And in test is produced, according to the formula of above-mentioned film, adopt the flat embrane method production technique of traditional BOPP, in process of production, BOPP film will contact with heating roller surface when longitudinal stretching, and PP draft temperature is greater than 120 degree, causes film when stretching and the generation adhesion of longitudinal stretching roller surface, and cannot produce.
The combined strength bination of BOPP film of the present invention and contrast film and paper heat posted and other the performance test results are in table two.Contrast film 8 is surperficial again by the structure that extrusion coated painting one deck VA content is the vinyl-vinyl acetate copolymer (EVA) of 18% in common BOPP film by traditional technology, 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 being compared by extrusion coated twice shaping pre-coating film from table two, and the laminating fastness of paper does not have difference substantially, even more excellent.And film of the present invention has the less feature of vertical lateral performance difference.
Now polypropylene double-way stretched film is the preparation of flat embrane method substantially in the art, wherein adopts the technique of step drawing, therefore, vertical and horizontal performance has larger difference, as, longitudinal elongation is much larger than cross direction elongation, and vertical and horizontal elongation ratio is greater than 2.0.And the present invention adopts periosteum method to produce polypropylene double-way stretched film, closely, and vertical and horizontal elongation ratio is generally less than 2 to its vertical and horizontal performance, even lower, such as, be 1.5.
Unless otherwise noted, practice of the present invention will use the routine techniques of organic chemistry, polymer chemistry etc., obviously except describing especially in above-mentioned explanation and embodiment, other mode can also realize the present invention.Other aspect will within the scope of the present invention be with improve will be apparent to those skilled in the art in the invention.According to instruction of the present invention, many changes and change are feasible, and therefore it is within the scope of the present invention.
All patents mentioned in this article, patent application and technical paper are all attached to herein accordingly by quoting.
Namely DEG C as represented without special, the unit " degree " of the temperature occurred herein refers to degree Celsius.
Claims (21)
1. a polypropylene double-way stretched film, it has basic unit and the heat posted functional layer of coextru-lamination, 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 one or more in vinyl-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-ethyl acrylate copolymer, ethylene ionomer type polar polymer, ethylene-maleic acid graftomer, described component (A) is according to dsc, i.e. DSC test, its fusing point is lower than 95 degree;
Component (B) be selected from ethene and butylene copolymer, ethene and hexene copolymer, ethene and octene copolymer one or more, described component (B) is according to dsc test, and its fusing point is lower than 95 degree;
Wherein component (A) with in the ethylene copolymer of polar group, polar comonomers content in described ethylene copolymer of vinyl-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-ethyl acrylate copolymer, ethylene ionomer type polar polymer is 5%-25 % by weight, and in ethylene-maleic acid graftomer, maleic anhydride content is 0.1%-2%;
Wherein described in component (B), multipolymer is metallocene quasi-polyethylene, wherein in ethene and octene copolymer, octene content is being greater than 20 % by weight to being less than or equal between 40 % by weight, in ethene and hexene copolymer, ahexene content is being greater than 15 % by weight to being less than or equal between 40 % by weight, and in ethene and butylene copolymer, butene content is being greater than 15 % by weight to being less than or equal between 40 % by weight;
Wherein, the longitudinal tensile strain rate of described polypropylene double-way stretched film is less than 2 with the ratio of cross direction elongation, and described film functional layer surface tension is between 36-48 dynes per centimeter,
And described polypropylene double-way stretched film, for be prepared by following method, be said method comprising the steps of:
(1) by polyolefinic raw materials, auxiliary material is undertaken preparing and mixing by the basic unit of described polypropylene film and the composition of heat posted functional layer, sends into forcing machine processing plasticizing; Through circular first periosteum of annular machine capitiform, then cool;
(2) the first periosteum is heated to draft temperature;
(3) synchronous horizontal stretching and longitudinal stretching are carried out to the first periosteum, to predetermined stretch ratio and pre-determined thickness, form the second periosteum;
(4) cool the second periosteum rapidly, then carry out heat setting type process;
(5) surface tension adjustment is carried out to the surface of the second periosteum after heat setting type;
(6) cool;
(7) rolling and cutting.
2. the polypropylene double-way stretched film of claim 1, the longitudinal tensile strain rate of wherein said polypropylene double-way stretched film is less than 1.5 with the ratio of cross direction elongation.
3. the polypropylene double-way stretched film of claim 1, wherein said component (A) is according to dsc test, and its fusing point is lower than 90 degree.
4. the polypropylene double-way stretched film of claim 1, wherein said component (B) is according to dsc test, and its fusing point is lower than 90 degree.
5. the polypropylene double-way stretched film of claim 1, its base material is made up of homo-polypropylene, Co-polypropylene or its blend, according to ASTMD-1238, at 230 degree, test under 2.16 kilograms of conditions, the melting index of described base material is 0.5-15g/10 minute.
6. the polypropylene double-way stretched film of claim 1, wherein according to ASTMD-1238, at 190 degree, tests under 2.16 kilograms of conditions, is 0.5-30g/10 minute with the melting index of the ethylene copolymer of polar group described in component (A).
7. the polypropylene double-way stretched film of claim 1, in wherein said ethene and octene copolymer, octene content is being greater than 20 % by weight to being less than or equal between 30 % by weight.
8. the polypropylene double-way stretched film of claim 1, in wherein said ethene and hexene copolymer, ahexene content is being greater than 20 % by weight to being less than or equal between 30 % by weight.
9. the polypropylene double-way stretched film of claim 1, in wherein said ethene and butylene copolymer, butene content is being greater than 20 % by weight to being less than or equal between 40 % by weight.
10. the polypropylene double-way stretched film of claim 1, in wherein said ethene and butylene copolymer, butene content is being greater than 20 % by weight to being less than or equal between 30 % by weight.
The polypropylene double-way stretched film of 11. claims 1, wherein said metallocene quasi-polyethylene is according to ASTMD-1238, and at 190 degree, test under 2.16 kilograms of conditions, its melting index is 0.5-30g/10 minute.
Polypropylene double-way stretched film any one of 12. claim 1-4, described basic unit and functional layer are respectively one deck, two layers or three-decker, and wherein the component of each basic unit or each functional layer is identical or different.
The polypropylene double-way stretched film of 13. claims 12, wherein outermost basic unit, i.e. top layer, containing polypropylene and polyethylene, wherein polyethylene is high density polyethylene(HDPE), and polypropylene is homo-polypropylene or Co-polypropylene.
The polypropylene double-way stretched film of 14. claims 1, it is characterized in that described overall film thickness is 10 microns-50 microns, the thickness of described functional layer is 1-15 micron.
The polypropylene double-way stretched film of 15. claims 14, is characterized in that the thickness of described functional layer is 3-10 micron.
16. 1 kinds of overlay film paper, it contains polypropylene double-way stretched film any one of claim 1-15 and paper, wherein said polypropylene double-way stretched film comprises basic unit and heat posted functional layer, described functional layer and paper 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.
The overlay film paper of 17. claims 16, wherein said paper is the paper of paper blank or printing, when described paper is the paper of printing, the functional layer of described composite film material and the surface laminating of paper printing ink.
Polypropylene double-way stretched film any one of 18. claim 1-15 is for preparing the purposes of overlay film paper with paper heating compound.
19. 1 kinds of methods preparing the polypropylene double-way stretched film any one of claim 1-15, comprising:
(1) by polyolefinic raw materials, auxiliary material is undertaken preparing and mixing by the basic unit of described polypropylene film and the composition of heat posted functional layer, sends into forcing machine processing plasticizing; Through circular first periosteum of annular machine capitiform, then cool;
(2) the first periosteum is heated to draft temperature;
(3) synchronous horizontal stretching and longitudinal stretching are carried out to the first periosteum, to predetermined stretch ratio and pre-determined thickness, form the second periosteum;
(4) cool the second periosteum rapidly, then carry out heat setting type process;
(5) surface tension adjustment is carried out to the surface of the second periosteum after heat setting type;
(6) cool;
(7) rolling and cutting.
The method of 20. claims 19, wherein, the heat setting type of described step (4) is warming mill sizing.
The method of 21. claims 19 or 20, wherein the surface tension adjustment of step (5) is undertaken by corona treatment.
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| CN104669749B (en) * | 2013-11-29 | 2016-11-16 | 群力塑胶有限公司 | Polypropylene composite film, preparation method, purposes and composite paper-plastic material and preparation method |
| CN104212383B (en) * | 2014-09-12 | 2016-04-27 | 刘国富 | A kind ofly mould the preparation method that Film laminated internal layer pre-coating film sticks with glue agent and internal layer pre-coating film |
| CN105128370A (en) * | 2015-09-06 | 2015-12-09 | 安徽国风塑业股份有限公司 | Preparation method of high-flexibility BOPP (Biaxially-oriented Polypropylene) film |
| CN108384477A (en) * | 2018-03-16 | 2018-08-10 | 云南名博包装印刷有限公司 | A kind of heat-seal adhesive and the embossing aluminium foil epiphragma comprising it |
| CN110757926A (en) * | 2018-07-25 | 2020-02-07 | 泉州利昌新材料科技有限公司 | Synthetic paper |
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| CN110920192A (en) * | 2019-11-15 | 2020-03-27 | 安徽国风塑业股份有限公司 | Metalized double-sided corona BOPP extinction heat-sealing film and preparation method thereof |
| CN112123902A (en) * | 2020-09-02 | 2020-12-25 | 安徽国风塑业股份有限公司 | BOPP film capable of being directly compounded with paper and plastic and preparation method thereof |
| CN112109414A (en) * | 2020-10-26 | 2020-12-22 | 广东安德力新材料有限公司 | Thermal compounding method of polypropylene film layer |
| CN112474692A (en) * | 2020-10-29 | 2021-03-12 | 安徽皖升力环保股份有限公司 | Garbage landfill process of household garbage landfill |
| CN113580705B (en) * | 2021-07-29 | 2023-03-17 | 海南赛诺实业有限公司 | Ultralow-temperature heat-sealing wear-resistant BOPP film and preparation method thereof |
| CN114407462B (en) * | 2022-01-29 | 2024-03-08 | 昆山加浦包装材料有限公司 | Biaxially oriented polypropylene base film with high surface energy |
| CN115386170B (en) * | 2022-09-30 | 2023-08-08 | 天津金发新材料有限公司 | Polypropylene composite material with good paint adhesion and preparation and application thereof |
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