CN1136096C - Laminated film - Google Patents
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- CN1136096C CN1136096C CNB991261844A CN99126184A CN1136096C CN 1136096 C CN1136096 C CN 1136096C CN B991261844 A CNB991261844 A CN B991261844A CN 99126184 A CN99126184 A CN 99126184A CN 1136096 C CN1136096 C CN 1136096C
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Abstract
To enable superb appearance and outstanding finish with satisfactory oxygen barrier properties and good dependence upon humidity by laminating a polymeric gas barrier layer on at least one of the faces of a biaxially oriented polypropylene film with the coefficient of heat shrinkage at a specific temperature indicating a specific value or less in any direction. The coefficient of heat shrinkage at 150 deg.C of a base material film in the mechanical axis direction of the film and an orthogonal direction with the former, is 5% or less respectively. A biaxially oriented polypropylene film is used and a polymeric gas barrier layer is laminated on at least one of the faces of this film. The polymeric gas barrier layer is a composite polymer layer which is formed by applying a coating solution of a composition containing a water-soluble polymer, a metallic alkoxide and/or an alkoxide silicate and polycondensating the metallic alkoxide and/or the alkoxide silicate by a sol-gel process and drying/curing the polycondensation product.
Description
The present invention relates to use the novel stacked film of biaxially oriented polypropylene film (OPP film, i.e. oriented polypropylene film made in following brief note).More particularly, the present invention relates to a kind ofly have good gas barrier properties (air impermeability) and finished product good appearance, the stacked film that on packings such as food, uses as the gas barrier properties film for oxygen, water vapour, nitrogen etc.
The OPP film is owing to have performances such as secondary operations such as good processing properties, good mechanical strength, the transparency, moisture resistance, bag, and by extensively with being film for packaging.
Yet, the gas barrier properties of above-mentioned OPP film, particularly the gas barrier properties to oxygen is low, needs under the situation of this character for example packaging for foodstuff purposes, especially existing problems in purification packaging for foodstuff purposes is used in above-mentioned packing purposes.
Therefore, in order to make the OPP film oxygen etc. had gas barrier properties, the macromolecule vapour barrier that people make at water soluble polymers such as OPP film stacked vinylidene chloride resin in surface and polyvinyl alcohol resins.
And in order to obtain better gas barrier properties, Te Kaiping 4-345841, spy open flat 8-99390, the spy opens in the communiques such as flat 9-278968 and the flat 9-291251 of Te Kai and discloses a kind of stacked film, this stacked film is prepared as follows: the solidification compound that inorganic polymer that the polycondensation of metal alkyl oxide obtains and polyvinyl alcohol resin is formed sol-gel process, heat cure is condensed into the composition polymer layer, more this composition polymer layer is made the macromolecule vapour barrier and is layered on the thermoplastic resin film.
Yet above-mentioned macromolecule vapour barrier is layered in the stacked film that obtains on the OPP film, produces wrinkle during with the heat viscosity method bag on heat seal face, and the gas barrier properties of packaging bag is reduced.
And, forming on OPP film surface under the situation of above-mentioned composition polymer macromolecule vapour barrier, film shrinks, curls etc. during heat treatment, impairs the composition polymer layer as cured film, and the stacked film gas barrier properties that obtains is reduced, and perhaps produces problems such as bad order.
Therefore, it is basement membrane with the OPP film that the object of the invention is to provide a kind of, stacked thereon macromolecule vapour barrier is made stacked film, this stacked film can solve use because of the OPP film fully and cause outward appearance and finished product bad, badly thus cause oxygen barrier low, and make problems such as packaging bag gas barrier properties difference during bag because of the heat bonding wrinkle, and has good characteristic.
Other purpose of the present invention and advantage can be clearer and more definite by following explanation.
The inventor etc. have carried out further investigation repeatedly in order to finish above-mentioned purpose, and found that: the OPP film that is limited in certain limit with percent thermal shrinkage is made basement membrane, and stacked thereon macromolecule vapour barrier can address the above problem fully, thereby has finished the present invention.
That is to say, the invention provides a kind of stacked film, it is characterized in that be by the mechanical axis direction (MD) of film and with it the last 150 ℃ of following percent thermal shrinkages of the direction of quadrature (TD) all less than 5% biaxially oriented polypropylene film and at least thereon the stacked macromolecule vapour barrier of one side form.
As preferred implementation, it is bonding to the invention provides a kind of further enhancement macromolecule vapour barrier, and all more good stacked films such as gas barrier properties and durability.
That is to say,, the invention provides as preferred implementation:
(1) under nitrogen and/or carbon dioxide atmosphere, the stacked film that Corona discharge Treatment and/or flame plasma are handled is carried out on the OPP film surface of stacked macromolecule vapour barrier side,
(2) under nitrogen and/or carbon dioxide atmosphere, the OPP film surface of stacked macromolecule vapour barrier side is carried out after Corona discharge Treatment and/or flame plasma handle, on this surface, form tackifier coating stacked film and
(3) on the OPP film surface of stacked macromolecule vapour barrier side, have from acid modified polyolefin, contain the polyolefin of ethene and contain the layer that at least a polyolefin selected the polyolefin of butene-1 forms, and under nitrogen and/or carbon dioxide atmosphere, this laminar surface is carried out the stacked film of Corona discharge Treatment and/or flame plasma processing.
In addition, stacked film provided by the invention, on the macromolecule vapour barrier of OPP film-stack, stacked again other thermoplastic resin films, thereby make various performances such as durability and gas barrier properties be able to further raising.
The OPP film
Use the OPP film as basement membrane among the present invention.That is to say, because biaxial tension forms the polypropylene molecule orientation texture, so the OPP film is also good especially for the gas barrier properties of water vapour except having good mechanical strength, again with its on the measure combination of stacked macromolecule vapour barrier, thereby can show the comprehensive gas barrier properties of high level.
Essential condition of the present invention is, makes the OPP film that basement membrane uses, can be with MD under 150 ℃ of temperature and TD direction percent thermal shrinkage (the following percent thermal shrinkage that also simply is called sometimes) all less than 5% OPP film.
That is to say,, cause film bad order and gas barrier properties to reduce if said percent thermal shrinkage greater than 5%, when then heating for formation composition polymer layer afterwards, strengthens the amount of crimp of macromolecule vapour barrier thermal contraction generation.In addition, when heat bonding, also occur wrinkle easily, reduce and make the gas barrier properties of packaging bag.
In the communique of quoting in front, be the basement membrane of stacked macromolecule vapour barrier though disclose the use polypropylene screen, wherein to using the variety of issue that stacked film produced of OPP film, as mentioned above, but without any explanation.
That is to say, do not know, certainly let alone its solution even forefathers connect the problem that the present invention will solve.So being inventor etc., this solution at first puts forward.
The percent thermal shrinkage of above-mentioned OPP film is considered the outward appearance and the gas barrier properties of stacked film all must preferably less than 4%, be more preferably less than 3% less than 5% on MD and TD two directions.
In the present invention, the percent thermal shrinkage of OPP film is shown in embodiment described later, according to the method for putting down in writing among the JIS C2318, in 150 ℃ of MD that measure down and the percent thermal shrinkage value on TD two directions.
The OPP film that uses among the present invention just is not particularly limited as long as have above-mentioned percent thermal shrinkage, but should and create conditions according to the material resin kind that constitutes film, preferably uses the secondary workability etc. of mechanical performance, moisture resistance, stacked film all good.
For example, the OPP film that the present invention uses, the summit value (the following fusing point that also is called the OPP film) of utilizing differential scanning calorimetry method (following note is made DSC) to measure is if consider the hear resistance and the moisture resistance of film, preferably be in 160～180 ℃, more preferably be in 165～180 ℃ of temperature ranges.
The fusing point of above-mentioned OPP film then because percent thermal shrinkage increases, then the trend that moisture resistance reduces will occur in order to reach above-mentioned percent thermal shrinkage if be lower than 160 ℃, thereby bad.On the other hand, be higher than under 180 ℃ the situation, because of the OPP film is difficult to make not preferred.
Form the acrylic resin of OPP film among the present invention, can not have any restriction with known product.For example, can enumerate polypropylene homopolymer, the alpha-olefin outside the propylene such as ethene, 1-butylene, 1-amylene, 1-hexene, 4-methyl-1-pentene and random copolymer or the block copolymer and the mixture of polymers thereof of propylene.
In above-mentioned acrylic resin, be the acrylic resin that the percent thermal shrinkage that is suitable for above-mentioned OPP film and fusing point use, wherein the copolymerization ratio of alpha-olefin should be in 2 moles below the % beyond the propylene, preferably is in 1 mole below the %.Preferably use polypropylene homopolymer.And in above-mentioned acrylic resin, preferably use high crystalline acrylic resin (the following high crystalline PP resin that also is called), promptly use
13The crystalline isotaxy five unit marks of expression (ア イ Application Network チ Star ケ ペ Application Star De branch rate) that the C-NMR method is measured are in the acrylic resin of 0.950～0.995 (preferred 0.970～0.990).
Five above-mentioned unit marks are less than under 0.95 the situation, and the fusing point of OPP film is low, cause easily that percent thermal shrinkage increases or problem such as moisture resistance reduction.And under greater than 0.995 situation, the stretch process performance when making the OPP film descends.
Above-mentioned isotaxy five unit marks are meant the article of delivering according to people such as A.Zambelli on " Macromolecules " 13,267 (1980), according to
13Continuous five shared marks of the same spatial configuration of polypropylene units of the ownership quantitative assay at C-NMR peak.
Above-mentioned acrylic resin can be made with known method.For example, can enumerate use TiCl
3, carrier model TiCl
3, known polypropylene catalyst such as metallocene oxide catalyst, make the method for above-mentioned monomer polymerization.And after polymerization, also can decompose with peroxide etc. as required.
Above-mentioned polyacrylic DSC summit measured value (fusing point) is as if then preferred 155～165 ℃ of the hear resistance of considering film, more preferably 160～165 ℃.Acrylic resin with this fusing point can satisfy the requirement of OPP film to above-mentioned preferred fusing point.
And, the melt flow rate (following note is made MFR) under 230 ℃, if consider extrudability and stretch process when the OPP film is made, then preferred 1～10 gram/10 minutes, more preferably 3～6 grams are/10 minutes.
Under the prerequisite of not damaging effect of the present invention, can also in acrylic resin, mix other resins among the present invention.Be not particularly limited for the resin that will mix, for example can enumerate vistanexes such as polyethylene, polybutene, TPO paraffin, the TPO elastomer, hydrocarbon resins such as Petropols and terpene resin, the copolymer of ethene and vinylacetate, acrylate, acrylic monomers, and the mixture of forming by two or more these polymer etc.
In addition, under the prerequisite of not damaging effect of the present invention, also can in above-mentioned acrylic resin, mix antistatic additive, antifoggant, anti-blocking agent, antioxidant, light stabilizer, nucleus agent, lubricant as required and to give the known additives such as surfactant that lubricity and resistance to blocking are purpose.
Though the present invention is not particularly limited the thickness of OPP film, preferably in 5～100 mu m ranges, suitably select.
And above-mentioned OPP film both monofilm also can be multilayer film.As preferred embodiment, can enumerate for example is the monofilm of Main Ingredients and Appearance with the polypropylene homopolymer, and is main composition layer and is the multilayer film formed of main composition layer etc. with the random copolymer between the alpha-olefin outside polypropylene and the polypropylene with polypropylene homopolymer.
For above-mentioned multilayer film, consider factors such as percent thermal shrinkage, with polypropylene homopolymer be main composition the layer thickness should account for more than 70% of each layer gross thickness, more preferably account for more than 80%.
And the OPP film among the present invention, if consider the packing purposes, particularly in the purposes of using with the gas barrier properties film, should the preferably clear film.Specifically, haze value preferably is in below 15%, more preferably is in below 10%.
The manufacture method of OPP film
The OPP film that uses among the present invention, have above-mentioned percent thermal shrinkage, as described below, can adopt two-way pulling method successively of tentering and tentering two-way simultaneous pulling method, suitably make by suitable selection stretch process condition and hot relaxation processes condition.
For example, with regard to draw ratio, when adopting the two-way pulling method successively of tentering, the MD direction stretches 3～5.5 times, the TD direction stretch 7～11 times be suitable.If draw ratio MD direction is less than 3 times, the TD direction then reduces bad because of film mechanical strength (tensile modulus of elasticity etc.) less than 7 times.Otherwise, when the MD direction greater than 5.5 times, the TD direction is during greater than 11 times, and is bad because percent thermal shrinkage increases.
And the draw ratio when adopting tentering two-way simultaneous pulling method, MD direction and TD direction preferably are 4～8 times.Draw ratio is during less than 4 times, and the mechanical strength of film reduces, and percent thermal shrinkage increases when being higher than 8 times, so all bad.
As above-mentioned stretch process condition, it is very important adopting the temperature conditions that suppresses above-mentioned crystalline polypropylene resinoid orientation relatively, generally speaking draft temperature should be set under the relatively-high temperature.
For example, though draft temperature is slightly different because of the difference of film-making machine tool, for example adopt under the situation of the two-way pulling method successively of tentering, MD stretches and utilizes roll to carry out usually, when roll stretches to preferred 130～160 ℃ of the heating-up temperature of stretched sheet not, more preferably 140～155 ℃.When above-mentioned MD stretches,, then bad for the heating-up temperature of stretched sheet not because percent thermal shrinkage increases if be lower than 130 ℃, otherwise if be higher than 160 ℃ then the MD sheet material adhere on the roll, thereby also bad.
And, carry out the TD stretching with the two-way pulling method successively of tentering and in expander, carry out preferred 145～165 ℃ of the heating-up temperature when expander stretches, more preferably 150～160 ℃ usually.Heating-up temperature when above-mentioned TD stretches is if be lower than 145 ℃, and is then bad because percent thermal shrinkage increases, otherwise then the film albefaction is also bad if be higher than 165 ℃.
On the other hand, for the tentering two-way simultaneous stretches, preferred 145～165 ℃ of heating-up temperature, more preferably 150～160 ℃.Heating-up temperature during above-mentioned stretching is if be lower than 145 ℃, and is bad because percent thermal shrinkage increases, otherwise also bad if be higher than 165 ℃ of film albefactions.
After above-mentioned stretch process, should heat-treat relaxation processes, preferred heat-treat condition is: heat treatment several seconds under 160～180 ℃ of temperature and in the atmosphere gas～tens of seconds, all shrink about 1～8% in MD direction and TD direction, and the percent thermal shrinkage of OPP film is reduced in the desired extent.
Use above-mentioned high crystallization PP resinoid to do under the situation of raw material,, needn't do the processing of MD direction sometimes especially, only carry out above-mentioned hot relaxation processes and just can reach above-mentioned percent thermal shrinkage with regard to the TD direction as above-mentioned hot relaxation processes.And this hot relaxation processes also can be carried out in streamline after the TD stretch processing.
Macromolecule vapour barrier (composition polymer layer)
In the present invention, on above-mentioned OPP film stacked macromolecule vapour barrier so long as knownly just be not particularly limited.For example, can enumerate the water soluble polymer layer, and water soluble polymer and oxide polymer that metal alkoxide and/or silane oxide polycondensation obtain is formed with sol-gel process, make composition polymer layer that this water soluble polymer and oxide polymer condensation form etc. in case of necessity again.
Compare with the layer that is formed by water soluble polymer separately, wherein the gas barrier properties of composition polymer layer is good, gas barrier properties is little to the dependence of humidity, and burning property and disposability are all good than chloride class water soluble polymer, so very be suitable for the present invention's use.
The composition polymer layer, preferably by the partial hydrolysis condensation polymer of at least a alkoxide of selecting in metal alkoxide and the silane oxide and the mixture of water soluble polymer, the perhaps product between this partial hydrolysis condensation polymer and the water soluble polymer, perhaps the mixture of this partial hydrolysis condensation polymer, water soluble polymer and this product is formed.
Above-mentioned water soluble polymer is can dissolve fully or microdispersed macromolecular compound in water under the normal temperature.Its instantiation, can enumerate polyvinyl alcohol and derivative thereof, what will be obtained by many ketone reduction of carbon monoxide-ethene copolymer group shape is how pure, cellulose derivative such as carboxymethyl cellulose, hydroxyethylcellulose, starch based such as oxidized starch, etherification starch, dextrin, polyvinylpyrrolidone, polyacrylic acid, polymethylacrylic acid or ethene copolymers such as its ester, salt and copolymer thereof, perhaps these polymer are through carboxyl or silyl-modified modification functional polymer etc.
In these water soluble polymers, preferred use polyvinyl alcohol based polymer and derivative thereof, and more preferably use saponification degree greater than 75% polyvinyl alcohol, 40 moles of hydroxyls below the % by the polyvinyl alcohol of acetalation, vinyl alcohol units at copolymerization of ethylene alcohol such as the ethylene-vinyl alcohol copolymers more than 60% (below be called EvOH).
And, consider gas barrier properties and processing characteristics, the degree of polymerization of above-mentioned polyvinyl alcohol based polymer and derivative thereof, preferred 100～5,000, more preferably 500～3,000.
On the other hand, form the above-mentioned metal alkoxide and the silane oxide of composition polymer layer usefulness, so long as the enough sol-gel process polycondensations of energy form just being not particularly limited of oxidized metal compound or silicon oxide compounds.Specifically, can enumerate for example tetramethoxy-silicane, tetraethoxysilane, MTMS, ethyl trimethoxy silane, the isopropyl trimethoxy silane, butyl trimethoxy silanes etc. can form the silane oxide of silica, the tetramethoxy titanium, purity titanium tetraethoxide, methyl trimethoxy oxygen base titanium, four titanium butoxide, tetraisopropoxy titanium, methyl three titanium isopropoxides etc. can form the alkyl titanium oxide of titanium oxide, the tetramethoxy zirconium, the tetraethoxy zirconium, tetrabutyl zirconate, methyl trimethoxy oxygen base zirconium, methyl triethoxy zirconium, methyl three isopropoxy zirconiums etc. can form zirconic zirconium alkoxide, aluminium methoxide, aluminium ethoxide, aluminium isopropoxide, methyl diisopropoxy aluminium etc. can form the aluminium alkoxide of aluminium oxide, tetramethoxy magnesium, tetraethoxy magnesium, tetraisopropoxide magnesium etc. can form magnesian magnane oxide, the epoxy third oxygen MTMS, the 2-epoxy third oxygen ethyl trimethoxy silane, the 3-glycidoxy-propyltrimethoxy silane, 3-glycidoxy propyl group three butoxy silanes, (3,4-ethyoxyl cyclohexyl) methyl tripropoxy silane, 2-(3,4-ethyoxyl cyclohexyl) ethyl trimethoxy silane, 3-(3,4-ethyoxyl cyclohexyl) propyl trimethoxy silicane etc. has the silane oxide of epoxy radicals, the amino methyl triethoxysilane, 2-amino-ethyl trimethoxy silane, 1-amino-ethyl trimethoxy silane, the 3-TSL 8330, the 3-aminopropyltriethoxywerene werene, N-amino methyl amino MTMS, N-amino methyl-3-TSL 8330, N-(2-amino-ethyl)-3-TSL 8330, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane etc. has amino silane oxide, vinyltrimethoxy silane, vinyltriacetoxy silane, N-β-(N-vinyl benzyl amino-ethyl)-gamma-amino propyl trimethoxy silicane or its hydrochloride etc. have the silane oxide of vinyl, and one or more mixture such as the compound that replaced by halogen atom of the part alkoxyl of these metal alkoxides or silane oxide.
In above-mentioned metal alkoxide and silane oxide, preferred especially tetramethoxy-silicane, tetraethoxysilane, tetramethoxy titanium, purity titanium tetraethoxide, four titanium butoxide, tetraisopropoxy titanium, tetramethoxy zirconium, tetraethoxy zirconium, tetrabutyl zirconate, aluminium methoxide, aluminium ethoxide, aluminium isopropoxide, glycidoxy MTMS, the 2-epoxy third oxygen ethyl trimethoxy silane, 3-glycidoxy-propyltrimethoxy silane, 3-glycidoxy propyl group three butoxy silanes.
In the present invention, mix above-mentioned water soluble polymer and above-mentioned metal alkoxide and/or silane oxide, can obtain forming the composition of composition polymer layer usefulness by suitable selection.In this case, mixed proportion between above-mentioned water soluble polymer and above-mentioned metal alkoxide and/or the silane oxide, promptly form proportioning (water soluble polymer/metal oxide compound and/or the silane oxide between the water soluble polymer and metal oxide compound and/or silane oxide in the composite oxides of stacked film, weight %: weight %), should determine according to whether bringing into play good gas barrier properties, preferably be in 10/90～80/20 scope.If consider gas barrier properties and to the dependence of humidity, the aforementioned proportion in this composition polymer more preferably is in 20/80～70/30 scope.
The thickness of macromolecule vapour barrier is not particularly limited in the stacked film of the present invention, more than the preferred 0.1 μ m, more preferably more than the 0.3 μ m.And, more preferably be in below the 6 μ m if, then preferably be in below the 10 μ m from the considerations such as suitability for secondary processing of economy with performance stacked film effect.
Macromolecule vapour barrier (the formation method of composition polymer layer)
In the manufacture method of stacked film of the present invention, the formation method of macromolecule vapour barrier is not particularly limited, so long as known formation method just can adopt.
For example, formation for the composition polymer layer, generally the method that can adopt is: on above-mentioned at least one surface of OPP film with particular thermal shrinkage factor, coating contain water soluble polymer and metal alkoxide and/coating fluid that the composition of silane oxide is made, with sol-gel process make metal alkoxide and/the silane oxide polycondensation after, be dried curing.
The composition of above-mentioned coating fluid, so long as can form before the dry solidification above-mentioned metal alkoxide and/condensation polymer of silane oxide, just be not particularly limited.For example, can enumerate make above-mentioned water soluble polymer and metal alkoxide and/composition of the liquid that silane oxide uniform dissolution or dispersion in solvent form, perhaps to the composition that wherein adds hydrolytic reagent as required, again or make metal alkoxide and/or silane oxide, add hydrolytic reagent in case of necessity, after being made as the oxide polymer of condensation polymer in advance, with the water soluble polymer uniform dissolution or be dispersed in composition that obtains in the solvent etc.
Above-mentioned hydrolytic reagent so long as knownly just can use, is not particularly limited.Its instantiation can be enumerated inorganic acids such as hydrochloric acid, organic acids such as acetate, perhaps aqueous alkalis such as NaOH, ammonia, organic amine compound.Water also can be brought into play the function of hydrolytic reagent.
As the coating method of above-mentioned coating fluid, in implementation process of the present invention, preferably adopt the solution or the solvent that can form film coating at a high speed to disperse coating process.If enumerate the instantiation of this coating method, then preferably adopt the runner gravure method, oppositely coating process (リ バ-ス コ-ト), spraying process, contact coating method (and キ Star ス コ-ト), mould be coated with method (ダ イ コ-ト), meter coating process (メ リ Application グ バ-コ コ-ト) and and be coated with the runner gravure method of method (チ ャ Application バ-De Network -) or curtain formula curtain coating etc. with cutter, coating fluid is coated in the coating method on OPP film surface.
Dissolving and disperse the high molecular solvent of the above-mentioned aqueous solution, water or water-lower alkyl alcohol mixed solvent is suitable for.If consider cementability and productivity ratio, the water-soluble-lower alkyl alcohol mixed solvent of wherein preferred use.
Said lower alkyl alcohol, the alcohol of preferred 1～3 carbon atom, specifically particular methanol, ethanol, normal propyl alcohol or isopropyl alcohol.The mixed proportion of water-alcohol should suitably be selected in 99/1～20/80 scope.
In order to improve the adaptability of coating on the OPP film, also can in the scope that does not influence coating fluid stability, in above-mentioned coating fluid, add other water-soluble organic compounds.Specifically, except the above-mentioned lower alcohol that uses as solvent, can also enumerate di-alcohols such as ethylene glycol, propane diols, ethylene glycol derivatives such as methyl Cellosolve, ethyl Cellosolve and normal-butyl Cellosolve, polyalcohols such as glycerine, paraffin, ethers such as dioxane, three oxygen, six rings, ester classes such as ethyl acetate, ketones such as methyl ethyl ketone, aqueous based tackifier coating such as water-based isocyanate, polymine and epoxy resin.
In stacked film manufacture method of the present invention, make the method for the coating fluid drying on the OPP film, so long as known method just can adopt.Specifically, can enumerate one or more heating means such as hot-rolling contact method, thermal medium (air, wet goods) contact method, infrared ray heating and microwave heating method.
If consider from aspects such as finished product such as film outward appearance and drying efficiencies, preferred hot-air contact method and infrared ray heating in said method.
Especially, when above-mentioned composition polymer layer is dry,, then preferably in the following temperature range of basement membrane fusing point, adopt the temperature more than 100 ℃ to carry out drying if consider the appearance and the drying efficiency of gas barrier properties.Preferred lower limit temperature is 110 ℃, particularly 120 ℃.And preferred ceiling temperature should hang down 10 ℃ than the fusing point of basement membrane, particularly low 15 ℃.
The time that above-mentioned drying is required is if consider vapour barrier and drying efficiency, between then preferred 5 seconds～10 minutes, between more preferably 10 seconds～5 minutes.
And, in above-mentioned dry front and back, can also carry out high energy radiation exposures such as ultraviolet ray, X-ray, electron ray in case of necessity.Be mixed with under the situation of utilizing high-energy ray irradiation polymerization composition, it is suitable carrying out the high-energy ray irradiation.
More than just with the situation of composition polymer layer as the macromolecule vapour barrier, its formation method has been described, but the formation method of water soluble polymer layer is not limited to according to known method.Generally speaking, the method that adopts usually is: above-mentioned water soluble polymer is dissolved in the above-mentioned solvent makes coating fluid, according to above-mentioned coating method it is applied then.
The modification of OPP film
In order further to improve the cementability of composition polymer layer and OPP film, make the stacked film that obtains have higher gas barrier properties and durability, as preferred implementation of the present invention, the invention provides the stacked film of a kind of use through the above-mentioned OPP film of various surface-treateds.
That is to say,, the invention provides as preferred implementation:
(1) under nitrogen and/or carbon dioxide atmosphere, the stacked film that Corona discharge Treatment and/or flame plasma are handled is carried out on the OPP film surface of stacked macromolecule vapour barrier one side,
(2) under nitrogen and/or carbon dioxide atmosphere, the OPP film surface of stacked macromolecule vapour barrier one side is carried out after Corona discharge Treatment and/or flame plasma handle, on this upper surface, be formed with tackifier coating stacked film and
(3) on the OPP film surface of stacked macromolecule vapour barrier one side, have from acid modified polyolefin, contain the polyolefin of vinyl and contain the layer that at least a polyolefin selected the polyolefin of butene-1 forms, and under nitrogen and/or carbon dioxide atmosphere, it is carried out the stacked film of Corona discharge Treatment and/or flame plasma processing.
In above-mentioned (1) stacked film the OPP film is implemented Corona discharge Treatment, the atmosphere gas during processing must be nitrogen and/or carbon dioxide, preferred nitrogen from economic considerations.
And the oxygen concentration in nitrogen and/or carbon dioxide atmosphere gas, consider from the cementability between OPP film and the composition polymer layer, preferably less than 5 volume %, be more preferably less than 3 volume %.
According to voltage * electric current/(electrode width * film speed of service) (watt-minute clock/rice
2) the Corona discharge Treatment density that calculates, preferred 5～100 watt-minutes clock/rice
2, more preferably 10～70 watt-minutes clock/rice
2
That is to say, OPP film surface-treated density is lower than 5 watt-minutes clock/rice
2Occasion under, because of cementability reduces badly, and be higher than under the situation of 100 watt-minutes clock/rice 2, produce adhesion between the OPP film, and on the film width, will produce the processing uneven phenomenon, so also bad.
The humidex of OPP film treated side after above-mentioned Corona discharge Treatment, preferred 40～55 milli ox/rice, more preferably 45～50 milli ox/rice.When humidex is lower than 40 milli oxen/rice, because of the cementability reduction not preferred; Otherwise, produce adhesion between the OPP film when being higher than 55 milli oxen/rice, so and to produce the processing uneven phenomenon on the film width also bad.The main cause of coating inequality and adhesive strength inequality when said processing inequality will become coating, thus bad.
On the other hand, in the stacked film of above-mentioned (1), it is the processing method of pointing to OPP film surface winding-up flame plasma that said flame plasma is handled, said plasma is when imflammable gas such as natural gas, liquefied petroleum gas, propane gas, butane gas are burnt, and produces ionixedpiston and form in flame.
When this flame plasma was handled, the intensity that flame plasma is handled was slightly different because of the difference of processed OPP film, but preferably at 1～15 kilocalorie/meter
2Select more preferably 2～10 kilocalories/meter in the scope
2
That is to say, handle intensity and be lower than 1 kilocalorie/meter
2The time because and the cementability between the composition polymer layer that obtains of sol-gel process descend and not preferred, otherwise be higher than 15 kilocalories/meter
2Situation under, the OPP film produces the thermal contraction wrinkle, perhaps it is believed that because of cooling off the bad end thermal contraction thickening phenomenon (following note is made the thick phenomenon in limit) that causes easily, so also bad.
Above-mentioned processing intensity, can according to the unit interval (minute), the burner length (length identical) (rice) of flame energy with the suitable burner rating of unit burner length (rice) (kilocalorie/rice minute) expression, the film speed of travel (meter/minute), film width (rice) and use when the said film processing with the film width, utilize following formula (1) to calculate.
When above-mentioned flame plasma was handled, the distance between the end of flame internal flame and processed this object being treated of OPP film was from preferred 1～5 millimeter of the considerations such as stability of processing horizontal, more preferably 1～3 millimeter.
And when flame plasma is handled, generally be to make under film one side and the chill roll state of contact and film is under the state of walking winding-up flame plasma torch on the another side of this film.This moment, the temperature of chill roll should be selected between room temperature～60 ℃, preferably selected between 30～45 ℃.
After above-mentioned flame plasma was handled, the humidex of OPP film treated side was preferably 35～65 milli ox/rice, more preferably 40～60 milli ox/rice, preferably 45～60 milli ox/rice.
This humidex is lower than under the situation of 35 milli ox/rice, because and the cementability between the sol-gel composition polymer layer reduces and bad, and when surpassing 65 milli oxen/rice, because of being easy to generate the wrinkle that the film thermal contraction causes, produce adhesion between the basement membrane, so also bad.
Through the surface smoothness (Ra) of flame plasma processing OPP film treated side, from preferred 0.5～100 nanometer of cementability, more preferably 1～80 nanometer, preferably 2～50 nanometers.
Above-mentioned Corona discharge Treatment and flame plasma are handled, and both can distinguish and handle OPP film surface separately, also can simultaneously and use.And processing sequence is preferably carried out flame plasma at last and is handled.
And, the surface treatment of the OPP film that the present invention uses, in the scope that does not influence effect of the present invention, also can with other processing and the usefulness beyond the above-mentioned processing.Specifically, can enumerate plasma treatment, electron ray treatment with irradiation and the ultraviolet irradiation processing etc. of excited inert gas.
After passing through on the treated side of above processing, forming the composition polymer layer according to the method described above, can obtain the preferred stacked film of all good the present invention of gas barrier properties and durability.The formation of tackifier coating
The stacked film of above-mentioned (2) is that the method for utilization stacked tackifier coating on the treated side of the OPP film of above-mentioned Corona discharge Treatment of process and/or flame plasma processing makes the stacked film that forms higher, the more stable composition polymer layer of adhesive strength on it.
Form the tackify coating that above-mentioned tackifier coating uses,, can use so long as known product just are not particularly limited.For example can enumerate tackify coating such as isocyanates, polyurethanes, polyesters, polyethyleneimine: amine, polybutadiene, TPO, alkyl titanate ester.From effect of the present invention, the tackify coating of preferred isocyanate class, polyurethanes and polyesters wherein; And more preferably a kind of and two or more mixture and product in isocyanate compound, polyurethane and the carbamate prepolymer, one or more mixture and product, perhaps their solution or dispersion liquid in polyester, the how pure and mild polyethers.
On the biaxially oriented polypropylene film treated side of handling at above-mentioned flame plasma, the method of stacked tackifier coating is not particularly limited, for plant-scale enforcement, preferred adopt following laminating method, promptly runner gravure method, reverse coating process, spraying process, contact coating method, mould are coated with method, meter coating process and and are coated with the runner gravure method etc. of method with cutter.
And the quantity of tackifier coating should be at 0.01～5 gram/rice according to dry weight basis
2Select preferred 0.1～2 gram/rice in the scope
2
On the treated side of above-mentioned processing, form the composition polymer layer according to the method described above after, can obtain all good stacked film of the present invention of a kind of gas barrier properties and durability.
The formation of acid modified polyolefin layer
The stacked film of above-mentioned (3) is, after forming the acid-modified polyolefin resin layer on the OPP film surface, handle by its surface being carried out above-mentioned Corona discharge Treatment and/or flame plasma, make the stacked film that forms higher, the more stable composition polymer layer of adhesive strength on it.
Constitute the resin of above-mentioned acid modified polyolefin layer, wait from cementability, preferably contain 0.01～15 weight % according to the total amount meter, more preferably 0.1～10 weight % derives from the monomeric unit of unsaturated organic acid acid anhydride.And, both can use the vistanex of sour modification separately, also can and use the vistanex and the vistanex of sour modification.
The above-mentioned monomeric unit content that derives from the unsaturated organic acid acid anhydride is as if being lower than 0.01 weight %, and then cementability reduces, and the transparency reduces under the situation of 10 weight % and surpass, so all bad.
The vistanex of above-mentioned sour modification, it is suitable using the polyolefin that unsaturated organic acid acid anhydride shown below or unsaturated organic acid acid anhydride and derivative copolymerization thereof or graft modification are formed; Specifically can enumerate unsaturated organic acid acid anhydride, unsaturated organic acid acid anhydride and derivative modified product thereof, sour modified polypropene, sour modified poly ethylene, acid ethene improved-propylene copolymer, acid be ethene improved-vinyl acetate co-polymer, acid be ethene improved-butylene copolymer and sour modified propylene-butylene copolymer etc.
Consider from the transparency and durability, wherein preferably use unsaturated organic acid acid anhydride, unsaturated organic acid acid anhydride and derivative modified sour modified polypropene thereof.
MFR for above-mentioned acid-modified polyolefin resin is not particularly limited, but considers to surface migration and processing characteristics from polar group, should select preferred 5～150 grams/10 minutes at 0.1～150 gram in/10 minutes in the scope.
Above-mentioned unsaturated organic acid acid anhydride can specifically be enumerated acid anhydrides such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid.And, the also anhydride ester derivs that can and obtain with above-mentioned acid anhydrides and glycol, amino alcohol, diamines etc.Be not particularly limited for above-mentioned glycol, amino alcohol, diamines etc., for example can enumerate glycol such as ethylene glycol, propane diols, alkamines such as ethylaminoethanol, amino butanol, two amines such as ethylenediamine, diaminobutane etc.
In the acid-modified polyolefin resin layer that the present invention uses, the vistanex as mixing with above-mentioned acid-modified polyolefin resin can use polyolefin such as polypropylene, polyethylene, ethene-alpha-olefin copolymer, is not particularly limited.But from the transparency and hear resistance consideration, wherein the optimization polypropylene homopolymers, contain ethylene-propylene random copolymer that 0.1～15 mole of % comes from ethylene monomer unit, contain ethylene-propylene-1-butene random copolymer that 1～15 mole of % comes from ethene and 1-butene monomer units.
The MFR of said polyolefins resin considers from extruding processing characteristics, should select preferred 1～10 gram/10 minutes at 0.1～20 gram in/10 minutes in the scope.
The thickness ratio of above-mentioned acid-modified polyolefin resin layer is not particularly limited, but if consider from cementability, processability and cost aspect, should suitably select preferred 5～30% in 1～50% scope.
And, in the stacked film of above-mentioned (3), handle at Corona discharge Treatment and/or flame plasma that above-mentioned acid modified polyolefin layer is done, carry out under the condition that describes in detail at (1) stacked film above being preferably in, make the humidex of Corona discharge Treatment post processing face reach 40～55 milli ox/rice, preferably reach 45～50 milli ox/rice.
Through on the treated side of above processing, form the composition polymer layer according to the method described above, can obtain all good stacked film of the present invention of gas barrier properties and durability.
The modification of stacked film (three layers)
Stacked film of the present invention by further stacked any thermoplastic resin film again on the polymerizable compound within thing laminar surface, can provide a kind ofly except effect of the present invention, also has the stacked film of various functions.
That is to say that the present invention can provide:
(4) on the one side of percent thermal shrinkage, be laminated with the macromolecule vapour barrier less than 5% OPP film, and the stacked film that further stacked thermoplastic resin film forms on this vapour barrier surface.
In this (4) stacked film, thermoplastic resin as the use of thermoplastic resin film material resin, can enumerate for example polyethylene, vistanexes such as polypropylene, PETG, polybutylene terephthalate (PBT), poly-2, polyester resins such as 6-naphthalene diacid glycol ester, nylon 6, nylon 12 polyamide-based resins such as grade, polyvinyl chloride, ethylene-vinyl acetate copolymer or its are saponified, polystyrene, Merlon, polysulfones, polyphenylene oxide, polyphenylene sulfide, aromatic polyamides, polyimides, polyamidoimide, polyacrylonitrile, polyvinyl alcohol etc. and copolymer thereof.
Embodiment with antistatic backing
Stacked film of the present invention, except above-mentioned gas barrier properties, for prevent because of content attached to causing the bad problem of heat seal to produce on the packaging material, preferably with the intrinsic resistance on stacked film surface, be adjusted to surperficial intrinsic resistance log Ω as sealing surface=below 11.
That is to say that the present invention also provides:
(5) a kind of stacked film, this stacked film are to form by being laminated with the macromolecule vapour barrier on percent thermal shrinkage at least one surface less than 5% OPP film, at least one lip-deep intrinsic resistance log Ω=and below 11.
Above-mentioned (5) of the present invention stacked film can utilize known anti-static method to form the surface with this static electricity resistance.
For example, the method for coating antistatic agent on the stacked film surface, and the method etc. of in pleurodiaphragmatic in terspace material resin, mixing antistatic agent.
Above-mentioned antistatic agent is if from considering with aspects such as the adaptability of the compatibility of resin, heat endurance, physical property, environment, low costs, can suitably select one or more uses in known antistatic agent.The instantiation of above-mentioned antistatic agent, can enumerate for example fatty acid glyceride, the D-sorbite fatty acid ester, pentaerythritol fatty ester, polyol fatty acid ester such as cithrol and polyglyceryl fatty acid ester class antistatic agent, the alkyl diethanol amine, alkyl amine antistatic agents such as alkyl diethanol amine fatty acid ester, the alkyl diglycollic amide class antistatic agent that diethanol amine and aliphatic acid form, the triakyl benzyl ammonium, cationic antistatic agents such as tetra-allkylammonium, alkylbenzenesulfonate, alkylsulfonate, alkyl sulfate, anionic species antistatic agents such as alkylphosphonic, alkyl betaine, amphion antistatic agents such as alkyl imidazoline etc.If consider from static electricity resistance and adhesive, wherein one or more antistatic agents in preferably glycerine fatty acid ester, D-sorbite fatty acid ester, alkyl diethanol amine, alkyl diethanol amine fatty acid ester and the alkyl diglycollic amide.And the carbon atom number of alkyl in above-mentioned aliphatic acid and the alkylamine is considered to be preferably 6～22, more preferably 12～20 from static electricity resistance.
When forming the stacked film of above-mentioned (5), best embodiment is the thermoplastic resin film of laminate surface intrinsic resistance log Ω=below 11 again on the macromolecule vapour barrier.
Concrete layer structure can be enumerated: the OPP film of macromolecule vapour barrier/surperficial intrinsic resistance log Ω=below 11, thermoplastic resin film/macromolecule vapour barrier/OPP the film of surface intrinsic resistance log Ω=below 11, the thermoplastic resin film of the OPP film/macromolecule vapour barrier/surperficial intrinsic resistance log Ω of surperficial intrinsic resistance log Ω=below 11=below 11 etc.
In these embodiments, for the situation that should prevent that content in the packaging for foodstuff from adhering to because of static and being used for bag packing purposes, it is suitable that the thermoplastic resin film of surperficial intrinsic resistance log Ω=11 below is used as diaphragm seal.
The thickness of above-mentioned thermoplastic resin film, preferred 5～100 μ m, more preferably 10～80 μ m.
The purposes of stacked film of the present invention, though be not particularly limited, as used for packing foods films such as gas barrier properties (oxygen barrier, every nitrogen with every carbon dioxide) films, be specially adapted to the food containing water packing with boiling, alembic sterilization processing film.Be not particularly limited for packaged article, specifically can be used to pack salt marsh, daily pickles, Boiled fish shellfish, konjaku, big Miso Soup, fish lamb, grilled fish volume, aquatic products processing product, hamburger, grape wine, sausage, ham, other poultry meat processed goods, cheese, butter, the cake made of glutinous rice, sold in sliced pieces, sea-tangle silk, curry, stew food such as food and packed meal in clear soup.In addition, also can be used among the packing purposes of branchs of industry such as medical treatment, electronics, chemistry and machinery such as agricultural chemicals, medicine, fertilizer, precise materials.
Embodiment
Below enumerate embodiment and reference examples explanation the present invention, but the present invention is not subjected to the restriction of these embodiment.
About the physical property of resin and film in following examples and the reference examples etc., measure in this specification in order to method down.
(1) the DSC main peak of material resin is measured
Put into the aluminium dish behind about 5～6 milligrams of samples of weighing, use the differential calorimeter in 20 ml/min stream of nitrogen gas, to be warmed up to 235 ℃, under this temperature, kept 10 minutes, then with 10 ℃/minute speed cool to room temperature from room temperature.After this, from obtain the main peak on the melting curve mensuration curve with 10 ℃ of/minute intensifications.
(2) the DSC main peak of film is measured
Put into the aluminium dish behind about 5～6 milligrams of samples of weighing, use differential calorimeter speed with 10 ℃/minute in 20 ml/min stream of nitrogen gas to be warmed up to 235 ℃, from obtaining the main peak on the melting curve mensuration curve from room temperature.
(3)MFR
Measure according to JIS K7210.
(4) five unit marks (mmmm value) and copolymer are formed
The system JNM-GSX-270 of use NEC (
13C-nmr frequency 67.8MHz), measure under the following conditions.
Mode determination: perhydro is uncoupled
Impulse amplitude: 7.0 microseconds (C45 degree)
Pulse-recurrence time: 3 seconds
Accumulative frequency: 10,000 times
Solvent: o-dichlorohenzene/heavy benzol mixed solvent (90/10 volume %)
Sample concentration: 120 milligrams/2.5 milliliters solvents
Measure temperature: 120 ℃
In this case, by measuring
13Mmmm five unit marks have been obtained at the division peak in C-NMR spectrum methyl district.And the ownership at peak, methyl district is according to people such as A.Zamberlli, and " Macromolecules " 13.267 (1980) measures.
(5) transparency (mist degree)
Measure according to JIS K6714.
(6) percent thermal shrinkage
According to JIS C2318, measured the percent thermal shrinkage under 150 ℃ in MD direction and the TD direction.
(7) oxygen barrier
According to JIS K7126 B method, (mocon company produces, and OX-TRAN100), at condition determination: 25 ℃ and relative humidity are to carry out under 0%, 80% and 90% atmosphere to use the oxygen permeability determinator.
(8) moisture resistance (water vapour vapour barrier)
According to JIS K7129 B method, use saturating wet determinator (mocon company produces, PERMATRAN-W TWIN), under 40 ℃ and 90% relative humidity atmosphere, made mensuration.
(9) outward appearance of coating caudacoria
Under the following condition of enumerating, behind coating and dry solidification on 30 centimetres of wide biaxially oriented polypropylene films, evaluate its outward appearance according to following benchmark.(condition)
Drying means: guide roller arch hot-blast spray nozzle blowing type
Application pattern: general bar coating machine (コ Application マ バ-コ--)
Coating speed: 18 meters/minute
Drying oven length: 6 meters
Design temperature: 100～140 ℃
Drying time: 20 seconds (film ocular estimate)
◎: almost do not find wrinkle and curling
Zero: can see a small amount of wrinkle and curling
*: can see a considerable amount of wrinkles and curling
(10) Corona discharge Treatment
The testing machine of the Corona discharge Treatment machine of springtime motor society system is equipped with in use, handles according to following condition.Corona discharge Treatment under the air atmosphere is also carried out with same testing machine.
The gas that feeds: nitrogen or nitrogen/carbon dioxide
Oxygen concentration: below the 5 volume %
The film speed of travel: 100 meters/minute
Electrode: aluminium 3 type electrodes
Electrode-intermembranous distance: 2.0 millimeters
Generator: the springtime system AGI-200 of electric society
Roll temperature before handling: 65 ℃
Effective width of handling: 1,000 millimeter
(11) flame plasma is handled
Use the flame plasma Processing Test machine that U.S. Off リ Application バ-Na-company produces, handle under the following conditions.
Fuel: natural gas (mixing air)
Burner rating: 328～853 kilocalories/meter minutes
(the card number that is equivalent to 1 meter wide burner per minute burning)
Distance between flame internal flame-film surface: 2 millimeters
The film speed of travel: 100 meters/minute
Chill-roll temperature: 38 ℃
Effectively handle width: 600 millimeters
(12) adhesion
The treated side and the opposing face of two basement membranes (12 * 12 centimetres) are overlapped, under the state of 10 kilograms of whole surperficial loadings, under 50 ℃ of 90% relative humidity atmosphere, placed 24 hours.Shear sample, make it to stay the part (go up lower clamp and respectively clamp a slice film) of 40 millimeters of length, wide 30 millimeters laps and clamp clamps, with cupping machine (draw speed: 100 mm/min, distance is 40 millimeters between the chuck) measure to shear peel strength, according to following standard evaluation adhesive.
Estimate and shear peel strength (gram per centimeter
2)
◎ is lower than 10
Zero more than or equal to 10, less than 30
* greater than 30
(13) surface smoothness (Ra)
The scanning type probe microscope (NanoScope IIIa) that uses デ ジ Le イ Application ス Star Le メ Application Star society to produce is measured according to following condition, obtains the fineness on center line surface according to mean value for several times.
Pattern: tapping type ( Star ピ Application グ モ-De) AFM
Sweep limits: 10 μ m * 10 μ m
Probe radius: 5～10nm
Probe material: monocrystalline silicon
Sweep speed: 1.5Hz
The free amplitude of cantilever (カ Application チ レ バ-): 1.5V
The adjustment point of cantilever: 1.1～1.3V
The resonant frequency of cantilever: 300kHz
(14) cementability
Use the bar coating machine, coating process applies coating fluid on the biaxially oriented polypropylene film surface by hand, and coating layer thickness was approximately 3 μ m when applied thickness should make drying, was dried.After placing more than one day under the room temperature, according to X dicing tape method (JIS K5400) middle body of the stacked film coat side that obtains is carried out disbonded test, according to its extent of exfoliation of following standard evaluation.
The 5:X cutting part is not peeled off
The 4:X cutting part is peeled off below 10%
The 3:X cutting part is peeled off ratio more than 10%, less than 30%
The 2:X cutting part is peeled off ratio more than 30%, less than 50%
The 1:X cutting part is peeled off ratio more than 50%, less than 100%
0:X cutting part 100% is peeled off
(15) sealing intensity
Use 5 * 200 millimeters heat sealing machines, between 150 ℃ of sealant surfaces, seal stacked film.Downcut the sample of 15 millimeters width from sample through 1 kg/cm, 2 heat-sealing pressure and 1.0 seconds condition lower seals such as heat-sealing time, under conditions such as the long sample of 100 mm/min draw speeds and 40 millimeters (spacing jig from), measured tensile strength with cupping machine, with this as sealing intensity.The mean value of getting five samples is as result of the test.
(16) five unit marks (mmmm value) and copolymer are formed
The system JNM-GSX-270 of use NEC (
13C-nmr frequency 67.8MHz), measure according to following condition.
Mode determination: perhydro is uncoupled
Impulse amplitude: 7.0 microseconds (C45 degree)
Pulse-recurrence time: 3 seconds
Accumulative frequency: 10,000 times
Solvent: o-dichlorohenzene/heavy benzol mixed solvent (90/10 volume %)
Sample concentration: 120 milligrams/2.5 milliliters solvents
Measure temperature: 120 ℃
In this case, by measuring the division peak in 13C-NMR spectrum methyl district, mmmm five unit marks have been obtained.And according to people such as A.Zamberlli, " Macromolecules " 13.267 (1980) carried out the mensuration of peak, methyl district ownership.
Embodiment 1
Use T shape mouth mould extruder, under 280 ℃ of heating and meltings, the Resin A shown in the table 1 is extruded into sheet, behind the chill roll cooling curing, with the warm-up mill stretching-machine in 4.4 times of 151 ℃ of longitudinal stretchings of sheet temperature, use then expanding cross directional stretch machine in 158 ℃ with 10.5 times of its cross directional stretch after, on one side 10 seconds of heat cure under 175 ℃ of environment temperatures,, obtain biaxially oriented polypropylene film Yi Bian carry out TD direction 8% relaxation processes.Corona discharge Treatment is carried out on the surface of biaxially oriented polypropylene film that obtains.The biaxially oriented polypropylene film evaluation result that obtains is shown among the table 2.
Then, 30 weight portion tetraethoxysilanes, 20 parts by weight of ethanol, 1 weight portion 2N hydrochloric acid and 4 weight parts waters are mixed, under room temperature, stirred 1 hour.Then add 3 weight portions γ-glycidoxy trimethoxy silane, 40 weight portion Application ア ノ-Le 20L (Japanese synthetic chemistry society system ethene-vinyl alcohol water/IPA solution) and 0.15 weight portion N, stir behind the N-dimethyl benzyl amine, make coating fluid A.
Use rod to be coated with machine above-mentioned coating fluid A is coated on the Corona discharge Treatment surface of above-mentioned biaxially oriented polypropylene film, making dried coating layer thickness is 3 μ m, is dried curing under the conditions shown in Table 3.The evaluation result of the stacked film that obtains is shown among the table 3.
Embodiment 2 and 3 and reference examples 1 and 2
Use the biaxially oriented polypropylene film shown in the table 2, except being dried under the conditions shown in Table 3 the curing, all the other obtain stacked film according to conditional operation similarly to Example 1.Evaluation result is shown among the table 3.
Reference examples 3
Except using Application ア ノ-Le 20L monomer as the coating fluid, operate similarly to Example 1, obtain stacked film.Evaluation result is shown among the table 3.
Table 1
| Resin | Copolymer is formed mole % | MFR gram/10 minutes | DSC summit ℃ | Five unit marks | Additive antiblocking agent parts by weight | |
| A | Noblen | - | 4 | 165 | 0.985 | M：0.05 |
| B | The propylene-ethylene random copolymer | Ethene: 0.2 | 3.2 | 163 | 0.0973 | M：0.05 |
| C | The propylene-ethylene random copolymer | Ethene: 0.5 | 3.5 | 158 | 0.930 | M：0.05 |
| D | The propylene-ethylene random copolymer | Ethene: 4 | 7 | 138 | - | M：0.05 |
M: spherical melamine resin particle (average grain diameter 1.5 μ m)
Table 2
| Kind | Material resin | DSC summit film ℃ | Thickness μ m | Percent thermal shrinkage MD/TD% | Mist degree % | Corona discharge Treatment face humidex milli ox/rice |
| a | A | 175 | 20 | 2.5/2.0 | 2 | 40 |
| b | B | 168 | 20 | 3.5/2.3 | 2 | 42 |
| c | C | 163 | 20 | 6/8 | 3 | 42 |
Table 3
| Basement membrane | The dry solidification condition | Oxygen barrier 0%RH/80%RH milliliter/rice 2Day atmospheric pressure | Water vapour block gram/rice 2Day atmospheric pressure | Outward appearance | |
| Embodiment 1 | a | 141 ℃ 2 minutes | 2/3 | 3.8 | ○ |
| Embodiment 2 | a | 131 ℃ 2 minutes | 3/4 | 4.2 | ◎ |
| Embodiment 3 | b | 136 ℃ 2 minutes | 3/4 | 5 | ○ |
| Reference examples 1 | c | 95 ℃ 2 minutes | 5/15 | 5.5 | ○ |
| Reference examples 2 | c | 131 ℃ 2 minutes | 4/6 | 5.5 | × |
| Reference examples 3 | a | 141 ℃ 2 minutes | 3/15 | 4.4 | ○ |
Embodiment 4
Use T shape mouth mould extruder, under 280 ℃ of heating and meltings, the Resin A shown in the table 1 is extruded into sheet, behind the chill roll cooling curing, with the warm-up mill stretching-machine in 148 ℃ with 4.4 times of its longitudinal stretchings, continue with expanding cross directional stretch machine behind 9.5 times of 139 ℃ of cross directional stretch, on one side 10 seconds of heat cure under 168 ℃ of environment temperatures,, obtain biaxially oriented polypropylene film Yi Bian carry out the relaxation processes of TD direction 8%.
Then, flame plasma is carried out on film one surface and handle (processing intensity: 6.8 kilocalories/meter
2), obtain the surface treatment basement membrane of 20 μ m.The evaluation result of the surface treatment basement membrane that obtains is shown among the table 4.
Then use rod to be coated with the coating fluid A that machine obtains embodiment 1, be coated on the treatment surface of the surface treatment basement membrane that obtains, making dried coating layer thickness is 3 μ m, is dried to solidify 2 minutes under 120 ℃, and the evaluation result of the surface treatment basement membrane that obtains is shown among the table 5.
Embodiment 5 and 6
Except surface treatment basement membrane shown in the use table 4, obtain stacked film similarly to Example 1.Evaluation result is shown among the table 5.
Embodiment 7
Use rod to be coated with machine, on the composition polymer laminar surface of the stacked film that embodiment 4 obtains, coating tackify coating is (according to the ratio of 100 weight portions/100 weight portions, the TM329/CAT-8B of Japan モ-ト Application society system is dissolved in the ethyl acetate, adjusting its concentration makes nonvolatile component reach 10 weight %), make dry weight reach 2 gram/rice
2, under 80 ℃, be dried then.
The LLDPE film that then the stacked 40 μ m of dry type do not stretch on above-mentioned tackifier coating has obtained stacked film.Evaluation result is shown among the table 5.
Embodiment 8
Outside the diaphragm seal CPP (140 ℃ of fusing points are the propylene-ethylene-1-butylene ternary atactic copolymer films that contains 3 moles of % ethene, 1 mole of %1-butylene) that uses 25 μ m, obtained stacked film similarly to Example 7.Evaluation result is shown among the table 5.
Reference examples 4
Except using the surface treatment basement membrane shown in the table 4, obtained stacked film similarly to Example 7.Evaluation result is shown among the table 5.
Reference examples 5
Except using the surface treatment basement membrane shown in the table 4, obtained stacked film similarly to Example 8.Evaluation result is shown among the table 5.
Table 4
| The surface treatment basement membrane | Resin | Surface treatment order humidex (condition) milli ox/rice | Surface smoothness (Ra) nanometer | Adhesion | Percent thermal shrinkage MD/TD% | Mist degree % |
| d | A | F handles (6.8) 54 | 3.0 | ◎ | 2.5/2.2 | 3 |
| e | B | N handles (50) 48 F and handles (7.3) 62 | 3.0 | ○ | 3.3/2.3 | 3 |
| f | A | F handles (6.2) 41 | 3.3 | ◎ | 2.8/3.0 | 3 |
| g | A | C handles (10) 40 | 4.2 | ○ | 3.0/3.0 | 3 |
| h | B | C handles (25) 47 | 4.8 | × | 3.4/3.4 | 3 |
C handles: Corona discharge Treatment under the air atmosphere is to handle density watt-minute clock/rice in ()
2
N handles: Corona discharge Treatment under the nitrogen atmosphere is to handle density watt-minute clock/rice in ()
2
F handles: flame plasma is handled, and in () is to handle intensity watt-minute clock/rice
2
Table 5
| The surface treatment basement membrane | Cementability | Oxygen barrier 80%RH milliliter/rice 2Day atmospheric pressure | Heat seal strength kilogram/15 millimeter | |
| Embodiment 4 | d | 4 | 3 | - |
| Embodiment 5 | e | 4 | 3 | - |
| Embodiment 6 | f | 3 | 3 | - |
| Embodiment 7 | d | 4 | 3 | 3.8 |
| Embodiment 8 | d | 4 | 3 | 2.6 |
| Reference examples 4 | g | 1 | 4 | 2.0 |
| Reference examples 5 | g | 1 | 4 | 1.5 |
Embodiment 9
Use T shape mouth mould extruder, under 280 ℃ of heating and meltings, the Resin A shown in the table 1 is extruded into sheet, behind the chill roll cooling curing, with 4.4 times of warm-up mill stretching-machine longitudinal stretchings, continue with behind 9.5 times of the expanding cross directional stretch machine cross directional stretch, on one side 10 seconds of heat cure under 168 ℃ of environment temperatures,, obtain biaxially oriented polypropylene film Yi Bian carry out the relaxation processes of TD direction 8%.
Then, flame plasma is carried out on film one surface handle (handle intensity: 6.8 kilocalorie/meter 2), obtain the surface treatment basement membrane of 20 μ m.
Then use rod be coated with machine with tackify coating (according to the ratio of 100 weight portions/100 weight portions, the TM329/CAT-8B of Japan モ-ト Application society system is dissolved in the ethyl acetate, adjusting its concentration makes nonvolatile component reach 10 weight %), hardened coating is on the treatment surface of the surface treatment basement membrane that obtains, be dried 5 minutes under 100 ℃, and then at room temperature place more than one day, obtained stacked film.The dry weight of tackifier coating is 2 gram/rice
2
Be coated with feed liquid A with what rod was coated with that method coating embodiment 1 obtains, making dried coating layer thickness is 3 μ m, is dried under 120 ℃ and solidifies 2 minutes, and the evaluation result of the stacked film that obtains is shown among the table 6.
Embodiment 10 and 11 and reference examples 6 and 7
Except surface treatment basement membrane shown in the use table 4, obtain stacked film similarly to Example 9.Evaluation result is shown among the table 6.
Embodiment 12
Except using another kind of tackify coating (promptly according to the ratio of 100 weight portions/6 weight portions, the AD335A/CAT-10 of Japan モ-ト Application society system is dissolved in 1: 1 mixed solvent of MEK/ toluene, adjusting its concentration makes nonvolatile component reach 10 weight %) outside, obtained stacked film similarly to Example 9, its evaluation result is shown among the table 6.
Embodiment 13
Use aboveground metal industry society system test coating machine No. 3, with tackify coating (according to the ratio of 100 weight portions/100 weight portions, the TM329/CAT-8B of Japan モ-ト Application society system is dissolved in the ethyl acetate, adjusting its concentration makes nonvolatile component reach 10 weight %) be coated on the surface treatment basement membrane treatment surface that method obtains similarly to Example 9, make its dry weight reach 1 gram/rice
2
Follow the coating A that runner gravure embodiment 1 obtains, make dried thickness reach 3 μ m.
And then stacked above-mentioned tackifier coating, make its dry weight reach 2 gram/rice
2, and the not stretching LLDPE film of the stacked 40 μ m of dry type thereon, obtain stacked film.Its evaluation result is shown among the table 6.
Embodiment 14
Except diaphragm seal CPP (140 ℃ of the fusing points that use 20 μ m, be the propylene-ethylene-1-butylene ternary atactic copolymer film that contains 3 moles of % ethene, 1 mole of %1-butylene) replace having obtained stacked film similarly to Example 13 outside the not stretching LLDPE film of 40 μ m.Evaluation result is shown among the table 6.
Reference examples 8
Except using the surface treatment film shown in the table 4, obtained stacked film similarly to Example 13.Evaluation result is shown among the table 6.
Reference examples 9
Except using the surface treatment film shown in the table 4, obtained stacked film similarly to Example 14.Evaluation result is shown among the table 6.
Table 6
| The surface treatment basement membrane | Cementability | Oxygen barrier 80%RH milliliter/rice 2Day atmospheric pressure | Heat seal strength kilogram/15 millimeter | |
| Embodiment 9 | d | 4 | 3 | - |
| Embodiment 10 | e | 5 | 3 | - |
| Embodiment 11 | f | 3 | 3 | - |
| Embodiment 12 | d | 4 | 3 | - |
| Reference examples 6 | g | 2 | 4 | - |
| Reference examples 7 | h | 3 | 4 | - |
| Embodiment 13 | d | 4 | 2 | 3.5 |
| Embodiment 14 | d | 4 | 3 | 2.5 |
| Reference examples 8 | g | 2 | 3 | 2.8 |
| Reference examples 9 | g | 1 | 4 | 2.0 |
Embodiment 15
Use T shape mouth mould extruder, under 280 ℃ of heating and meltings, the Resin A shown in the table 1 is extruded into sheet, behind the chill roll cooling curing,, obtained the simple tension film with 4.4 times of warm-up mill stretching-machine longitudinal stretchings.Use T shape mould extruder, (Sanyo changes into industrial production of maleic anhydride modified polypropene: the hybrid resin monomeric unit 0.5 weight % that derives from the unsaturated organic acid acid anhydride) (D: ユ-メ Star Network ス 1001=80/20 (weight %/weight %)) is extruded into sheet as the acid-modified polyolefin resin layer with the resin D shown in the table 1 and ユ-メ Star Network ス 1001 under 230 ℃ of heating and meltings, on the chill roll it being fitted on the above-mentioned simple tension sheet surface, obtain double-layer tablet.Then with behind 9.5 times of the expanding cross directional stretch machine cross directional stretch, on one side under 168 ℃ of atmosphere gas temperature 10 seconds of heat cure, carry out the relaxation processes of TD direction 8% on one side, obtain biaxially oriented polypropylene film.
Then, acid modified polyolefin layer one side surface carried out flame plasma and handle (processing intensity: 6.5 kilocalories/meter
2), obtained the 20 μ m surface treatment basement membrane i that table 7 is put down in writing.
On the treatment surface of the film that obtains, be coated with feed liquid A with what rod was coated with that device coating embodiment 1 obtains, making dried coating layer thickness is 3 μ m, is dried to solidify after 2 minutes under 120 ℃ to obtain stacked film.Evaluation result is shown among the table 8.
Embodiment 16 and 17 and reference examples 10
Except using resin shown in the table 1 and the surface treatment basement membrane shown in the table 7, obtain stacked film similarly to Example 15.Evaluation result is shown among the table 8.
Embodiment 18
Use T shape mouth mould extruder, under 280 ℃ of heating and meltings, the Resin A shown in the table 1 is extruded into sheet, behind the chill roll cooling curing,, obtained the simple tension film with 4.4 times of warm-up mill stretching-machine longitudinal stretchings.Use T shape mould extruder, hybrid resin (D/XR110T=80/20 (weight %/weight %)) with the resin D shown in the table 1 and Off マ-XR110T (Mitsui Chemicals society system propene-1-butene-1 copolymer) under 230 ℃ of heating and meltings is extruded into sheet, obtains double layer sheet on the chill roll it being fitted on the above-mentioned simple tension sheet surface.Then with behind 9.5 times of the expanding cross directional stretch machine cross directional stretch, on one side under 168 ℃ of atmosphere gas temperature 10 seconds of heat cure, carry out the relaxation processes of TD direction 8% on one side, obtain biaxially oriented polypropylene film.
Then, under nitrogen atmosphere, the one side of film is carried out Corona discharge Treatment (processing density: 48 watt-minutes clock/rice
2), then carry out flame plasma and handle the 20 μ m surface treatment basement membranes 1 that (handle intensity: 6 kilocalorie/meter 2) obtained table 7 record.Be coated with device with rod and apply the coating fluid A that embodiment 1 obtains on the film treatment surface that obtains, making dried coating layer thickness is 3 μ m, is dried under 120 ℃ to solidify after 2 minutes to obtain stacked film.Evaluation result is shown among the table 8.
Embodiment 19
Use multilayer T shape mouth mould extruder, under 280 ℃ of heating and meltings, with the resin B shown in the table 1, (Sanyo changes into industrial production of maleic anhydride modified polypropene: (D: ユ-メ Star Network ス 1010=80/20 (weight %/weight %) is extruded into sheet to the hybrid resin monomeric unit 0.5 weight % that derives from the unsaturated organic acid acid anhydride) to resin D shown in the table 1 and ユ-メ ッ Network ス 1010, behind the chill roll cooling curing, with 5 times of warm-up mill stretching-machine longitudinal stretchings, then with behind 9.5 times of the expanding cross directional stretch machine cross directional stretch, 10 seconds of heat cure under 168 ℃ of atmosphere gas temperature on one side, carry out the relaxation processes of TD direction 8% on one side, obtain biaxially oriented polypropylene film.
Then, under nitrogen atmosphere, the one side of film is carried out Corona discharge Treatment (processing density: 50 watt-minutes clock/rice
2), obtained the 20 μ m surface treatment basement membrane m that table 7 is put down in writing.Be coated with feed liquid A with what rod was coated with that device applies on the film treatment surface that obtains that embodiment 1 obtains, making dried coating layer thickness is 3 μ m, is dried to solidify after 2 minutes under 120 ℃ to obtain stacked film.Evaluation result is shown among the table 8.
Embodiment 20
Use aboveground metal industry system No3 test coating machine, be coated with feed liquid A, be coated on the treated side of the surface treatment basement membrane m that obtains similarly to Example 9, make dried coating layer thickness reach 3 μ m what embodiment 1 obtained.
Follow stacked tackifier coating (according to the ratio of 100 weight portions/100 weight portions, the TM329/CAT-8B of Japan モ-ト Application society system is dissolved in the ethyl acetate, adjusts its concentration and make nonvolatile component reach 10 weight %), make dry weight reach 2 gram/rice
2Then the LLDPE film that do not stretch of the stacked 40 μ m of dry type has thereon obtained stacked film.Evaluation result is shown among the table 8.
Embodiment 21
Except using 25 μ m diaphragm seal CPP to replace the LLDPE film that 40 μ m do not stretch and using the surface treatment basement membrane that method obtains similarly to Example 1, obtained stacked film similarly to Example 20.Evaluation result is shown among the table 8.
Table 7
| The surface treatment basement membrane | Resin | Surface treatment order humidex (billot) milli ox/rice | Surface smoothness (Ra) nanometer | Adhesion | Percent thermal shrinkage MD/TD% | Mist degree % |
| i | A/(D+ユ—メック ス)18/2 | F handles (6.5) 54 | 2.3 | ◎ | 3.5/4.0 | 4 |
| j | B/(D+ユ—メック ス)18/2 | 1. N handles (48) 48 2. F processing (7) 61 | 2.7 | ○ | 3.8/4.4 | 4 |
| k | A/(D+ユ—メツク ス)18/2 | F handles (5.8) 41 | 2.5 | ◎ | 3.2/3.5 | 4 |
| l | A/(D+フマ- XR110T)18/2 | 1. N handles (48) 48 2. F processing (6) 59 | 3.0 | ◎ | 4.5/4.6 | 4 |
| m | (D+ユ—メックス) /B/(D+ユ—メツク ス)2/16/2 | N handles (50) 52 | 3.7 | ○ | 4.5/4.3 | 4 |
| n | B/(D+ユ—メック ス)18/2 | C handles (23) 47 | 5.0 | × | 4.2/4.6 | 3 |
C handles: Corona discharge Treatment under the air atmosphere is to handle density watt-minute clock/rice in ()
2
N handles: Corona discharge Treatment under the nitrogen atmosphere is to handle density watt-minute clock/rice in ()
2
F handles: flame plasma is handled, and in () is to handle intensity watt-minute clock/rice
2
Table 8
| The surface treatment basement membrane | Cementability | Oxygen barrier 80%RH milliliter/rice 2Day atmospheric pressure | Heat seal strength kilogram/15 millimeter | |
| Embodiment 15 | i | 5 | 3 | - |
| Embodiment 16 | j | 5 | 3 | - |
| Embodiment 17 | k | 5 | 3 | - |
| Embodiment 18 | l | 5 | 3 | - |
| Embodiment 19 | m | 5 | 3 | - |
| Reference examples 10 | n | 3 | 4 | - |
| Embodiment 20 | m | 5 | 3 | 3.8 |
| Embodiment 21 | i | 5 | 3 | 3.0 |
Embodiment 22
With rod be coated with device with tackify coating (according to the ratio of 100 weight portions/100 weight portions, the TM329/CAT-8B of Japan モ-ト Application society system is dissolved in the ethyl acetate solvent, adjusting its concentration makes nonvolatile component reach 10 weight %), be coated on the treatment surface of the biaxially oriented polypropylene film shown in table 9 and 10 (X layer), make dry weight reach 2 gram/rice
2At 90 ℃ down after dry back 5 minutes, be coated with device with rod the feed liquid A that is coated with that embodiment 1 obtains is coated on this tackifier coating surface, be dried 5 minutes (Y layer) of curing under 120 ℃.Re-use in above-mentioned identical tackify coating, the thermoplastic resin film shown in the stacked table 9 of dry type and 11 (Z layer) has obtained stacked film on this solidified surface.The evaluation result that obtains stacked film is shown among the table 12.
Embodiment 23
Except using biaxially oriented polypropylene film shown in table 9～11 and thermoplastic resin film, operate similarly to Example 21, obtained stacked film.Evaluation result is shown among the table 12.
Reference examples 11
Except using Application ア ノ-Le 20L monomer as the smears, operate similarly to Example 21, obtained stacked film.Evaluation result is shown among the table 11.
Reference examples 12
モ Application モ リ ロ Na イ ト (Network ニ ミ ネ industry society system, Network ニ ピ ア F) is dispersed in ultrasonic wave makes concentration in the ion exchange water and reach 1 weight % (B liquid).Polyvinyl alcohol (Japanese synthetic chemistry society system, go-セ ノ-Le NL05) heating for dissolving is made the solution that concentration is 1 weight % (C liquid) in ion exchange water.B liquid is become to be coated with feed liquid with C liquid mixed in equal amounts.
Except using above-mentioned coating liquid, operate similarly to Example 21, obtained stacked film.Evaluation result is shown among the table 11.
Table 9
| Kind | Resin | Copolymer is formed mole % | MFR gram/10 minutes | DSC summit ℃ | Five unit marks |
| E | Polypropylene | - | 4 | 165 | 0.980 |
| F | Ethylene-propylene random copolymer | Ethene: 4 | 8 | 140 | - |
| G | Low density polyethylene (LDPE) | Butene-1: 7 | 2(190℃) | 120 | - |
Table 10
N handles: Corona discharge Treatment under the nitrogen atmosphere is to handle density watt-minute clock/rice in ()
2
| The surface treatment basement membrane | Resin | Surface treatment order humidex (condition) milli ox/rice | Surface smoothness (Ra) nanometer | Adhesion | Percent thermal shrinkage MD/TD% | Mist degree % |
| o | E | N handles (50) 47 | 3.0 | ◎ | 2.8/3.5 | 3 |
Table 11
| Kind | Material resin | Film thickness μ m | Mist degree % | Treatment surface humidex milli ox/rice |
| P: unstretching film | F | 30 | 3.5 | 40 |
| Q: unstretching film | G | 50 | 4 | 42 |
Table 12
| Resin bed X layer/Z layer | The Y layer thickness is done μ m | Oxygen barrier 0%RH/90%RH milliliter/rice 2Day atmospheric pressure | Water vapour block gram/rice 2Day atmospheric pressure | |
| Embodiment 22 | o/p | 2 | 2.5/9 | 3.0 |
| Embodiment 23 | o/q | 2 | 2.5/8 | 2.4 |
| Reference examples 11 | o/p | 2 | 4/25 | 3.7 |
| Reference examples 12 | o/p | 1 | 1/20 | 2.7 |
As mentioned above, stacked film of the present invention will show good oxygen barrier and moisture resistance under high humility.On the other hand, as reference examples 11, only use under the situation of water soluble polymer, and as reference examples 12, use stratiform to contain under the situation of amyl group compound resin, under high humility, can not have oxygen barrier and moisture resistance simultaneously.
Embodiment 24
Use contains polypropylene (the MFR4 gram/10 minute of 0.5 weight % tetradecanoic acid diglycollic amide as antistatic agent, 165 ℃ of fusing points, five unit marks 0.980) be raw material, under 280 ℃ of heating and meltings, be extruded into sheet with T pattern extruder, behind the chill roll cooling curing, use 4.4 times of warm-up mill stretching-machine longitudinal stretchings, and then with 9.5 times of expanding stretching-machine cross directional stretch, 10 seconds of heat cure under 168 ℃ of atmosphere gas temperature on one side then, carry out TD direction 8% relaxation processes on one side, obtained biaxially oriented polypropylene film.After this, under nitrogen atmosphere, Corona discharge Treatment is carried out on film one surface and (handle density 50 watt-minutes clock/rice
2), obtain percent thermal shrinkage MD/TD 3.2%/4.2%, humidex 48 milli ox/rice, the surface treatment film of 20 μ m.
On the treatment surface of this surface treatment basement membrane, be coated with device coating tackify coating (Japan モ-ト Application society system with rod, host AD335AE 100 weight portions/curing agent CAT-10 10 weight portions) after, be coated with feed liquid A with what rod was coated with that device coating embodiment 1 obtains, making dried coating layer thickness is 3 μ m.Carry out again with above-mentioned same processing after, stacked random polypropylene (MFR 7 grams/10 minutes that contain 0.3 weight % tetradecanoic acid diglycollic amide as antistatic agent of dry type on this coating surface, 140 ℃ of fusing points, ethylene contents 2 weight %) be raw material, 50 μ m, two surfaces un-stretched polypropylene films, obtained stacked film through Corona discharge Treatment (humidex 40 milli ox/rice (strength reason) and 37 are ox/rice (weak processing) in the least).Evaluation result is shown among the table 13.
And above-mentioned stacked film made packaging bag, and make un-stretched polypropylene film side be in the inboard, inner surface does not produce attachment phenomenon behind the wooden loose fillet of packing into.
Table 13
| Gross thickness μ m | Oxygen permeability 0%RH/90%RH | Surface intrinsic resistance log Ω | |
| Embodiment 24 | 75 | 1/5 | 10.8 |
Stacked film of the present invention is a kind of like this stacked film, it is a basement membrane with specific biaxially oriented polypropylene film, by at least one surface of this basement membrane, the stacked composition polymer layer that specific composition polycondensation is obtained with sol-gel processing, not only oxygen barrier and oxygen barrier are all good to the dependence of humidity, and behind coating processing and the stacked diaphragm seal, has good finished product outward appearance through heat-sealing processing.Therefore, stacked film of the present invention not only is suitable for using as the trapping film, and can be widely used as the used for packing foods film.
Claims (8)
1, a kind of stacked film, it is characterized in that being by the mechanical axis direction of film and with it on the direction of quadrature 150 ℃ of following percent thermal shrinkages all less than 5% biaxially oriented polypropylene film and stackedly on the one or both sides thereon form with the macromolecule vapour barrier.
2, according to the described stacked film of claim 1, it is characterized in that wherein said macromolecule vapour barrier is by the partial hydrolysis condensation polymer of one or more alkoxides of selecting in metal alkoxide and the silane oxide and the mixture of water soluble polymer, the perhaps product between this partial hydrolysis condensation polymer and the water soluble polymer, perhaps the mixture of this partial hydrolysis condensation polymer, water soluble polymer and this product is formed.
3, according to the described stacked film of claim 1, it is characterized in that constituting the polypropylene of biaxially oriented polypropylene film, use
13The isotaxy five unit marks that the C-NMR method is measured are 0.95～0.995.
4, according to the described stacked film of claim 1, it is characterized in that biaxially oriented polypropylene film surface to said stacked macromolecule vapour barrier side, under nitrogen and/or carbon dioxide atmosphere, carry out corona discharge and/or flame plasma and handle.
5, according to the described stacked film of claim 1, the biaxially oriented polypropylene film surface that it is characterized in that wherein said stacked vapour barrier side, under nitrogen and/or carbon dioxide atmosphere, after Corona discharge Treatment and/or flame plasma processing, be formed with tackifier coating in its surface.
6, according to the described stacked film of claim 1, it is characterized in that on the two-way polypropylene screen surface of wherein said stacked vapour barrier side, have from acid modified polyolefin, contain the polyolefin of ethene and contain the formed layer of one or more polyolefin of selecting the polyolefin of butene-1, and handle through Corona discharge Treatment and/or flame plasma under nitrogen and/or carbon dioxide atmosphere on the surface of this layer.
7,, it is characterized in that on the surface of said macromolecule vapour barrier, also being laminated with the thermoplastic resin rete according to the described stacked film of claim 1.
8, according to the described stacked film of claim 1, the surperficial intrinsic resistance log Ω that it is characterized in that one of them or two surfaces is less than 11.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP359882/1998 | 1998-12-18 | ||
| JP35988298 | 1998-12-18 |
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| Publication Number | Publication Date |
|---|---|
| CN1262995A CN1262995A (en) | 2000-08-16 |
| CN1136096C true CN1136096C (en) | 2004-01-28 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB991261844A Expired - Fee Related CN1136096C (en) | 1998-12-18 | 1999-12-17 | Laminated film |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN1136096C (en) |
| TW (1) | TW490392B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1329185C (en) * | 2003-01-06 | 2007-08-01 | 东丽株式会社 | Laminated film and method for producing same |
| JP2009244258A (en) * | 2008-03-11 | 2009-10-22 | Sumitomo Chemical Co Ltd | Discriminating technique of high polymer compound membrane |
| WO2010074050A1 (en) * | 2008-12-25 | 2010-07-01 | 東海ゴム工業株式会社 | Transparent laminated film and method for producing the same |
| WO2014204625A1 (en) * | 2013-06-20 | 2014-12-24 | Exxonmobil Chemical Patents Inc. | Salenol catalyst |
| CN105408114B (en) * | 2013-07-23 | 2017-09-22 | 东洋纺株式会社 | Heat-sealable polypropylene is laminated oriented film |
| CN103640294B (en) * | 2013-11-28 | 2015-08-12 | 无锡合众信息科技有限公司 | A kind of compound package material |
| KR102242709B1 (en) * | 2014-04-15 | 2021-04-22 | 도레이 카부시키가이샤 | Layered film and process for producing layered film |
| KR102172867B1 (en) * | 2015-12-03 | 2020-11-02 | 미쓰이 가가쿠 토세로 가부시키가이샤 | Process release film, its use, and manufacturing method of resin-encapsulated semiconductor using the same |
| MX2021004089A (en) * | 2018-10-09 | 2021-08-19 | Sunallomer Ltd | Polypropylene sheet production method. |
| JPWO2020196301A1 (en) * | 2019-03-22 | 2020-10-01 |
-
1999
- 1999-12-15 TW TW88122026A patent/TW490392B/en not_active IP Right Cessation
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| TW490392B (en) | 2002-06-11 |
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