CN101024318A - Polypropylene resin laminated film and its manufacturing method - Google Patents
Polypropylene resin laminated film and its manufacturing method Download PDFInfo
- Publication number
- CN101024318A CN101024318A CNA2006101723588A CN200610172358A CN101024318A CN 101024318 A CN101024318 A CN 101024318A CN A2006101723588 A CNA2006101723588 A CN A2006101723588A CN 200610172358 A CN200610172358 A CN 200610172358A CN 101024318 A CN101024318 A CN 101024318A
- Authority
- CN
- China
- Prior art keywords
- film
- resin
- polypropylene
- sealant
- polypropylene resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Laminated Bodies (AREA)
Abstract
The invention provides polypropylene resinoid film membrane, which made up from polypropylene resinoid, and it is use gas-phase method, it is keen price and highly effective, good at nonstick and glider, While coiling to be coil the film membrane convolve is crease-resist, while bag forming and printed processing the working quality is well. The polypropylene resinoid laminate film in this invention laminate seal course which use polyolefin resinoid as body on positive and negative faces of base which use polypropylene resinoid as body. Furthermore, the polypropylene resinoid which constitutes foot layer and seal course is produced by gas-phase method. Furthermore, adjust it and make sure the coefficient of dynamic friction, air aerofluxus exponential and brume degree values which mensurated at 40 degree centigrade satisfy the enactment conditional.
Description
Technical field
The present invention relates to packaging film, particularly relate to and have anti-corona property, and sliding, adhesion inhibiting properties and the transparency are good, are suitable for packing comprising that vegetables, piece root, fruit, flowers and plants, flowers and trees, mushroom class, fish, meat etc. require the film of the plant of high freshness or the raw and fresh food of animal class (following these are called raw and fresh food).
Background technology
The film of being made by polyolefin resin has obtained extensive use as the packing material that with food is the various article of representative.Particularly polyacrylic film is because excellences such as food hygiene such as optical property, barrier properties for gases, odorless such as mechanical properties, the transparency, gloss, is center and extensive use with the field of used for packing foods therefore.But the polypropylene-based resin film has following shortcoming: adhesion inhibiting properties is poor, is easy to generate mutually bonding phenomenon (so-called adhesion phenomenon) of film during with film overlay, and operability such as packing is significantly descended.
In addition, as the method that prevents the polypropylene-based resin film blocking, organic based fine particles such as the mineral-type micropowder of representative or cross-linked polymer in film compounding have been proposed are as the method for so-called anti-blocking agent and the method for carrying out compounding with antiseize pastes such as fatty acid amides with silica.
In addition, add man-hour in that the polypropylene-based resin film with high anti-corona property is carried out bag, use on laminated with the method for polyolefin resin as the sealant of main body with the surface of polypropylene-based resin as the basic unit of main body.In addition, when like this in the basic unit that forms by propylene resin during the laminated sealant that forms by polyolefin resin, the bag of processing in order to make reveals enough intensity, use low-melting polyolefin resin to form to use resin use low-melting polyolefin resin to become the like this slip that makes film, the main cause of the further variation of adhesive as sealant more.As the method for eliminating this rough sledding, proposed in sealant forms with resin, to add the method (patent documentation 1) of inert particulates such as organic polymer particulate with setting particle diameter and mineral-type particulate.
Patent documentation 1: the spy opens the 2003-237827 communique
On the other hand, acrylic resin utilized so-called solvent method in the past, by in the presence of catalyst that titanium trichloride-the organo-aluminum compound isoreactivity is not too high, propylene polymerization being obtained, but polyolefinic polymerization catalyst is being updated, develop several high activated catalysts, its result can utilize so-called vapor phase method, makes acrylic resin more at a low price, efficiently.But, the acrylic resin that adopts above-mentioned vapor phase method to use high activated catalyst to obtain, its average grain diameter is big, narrow diameter distribution, powder content is few, when therefore in resin, adding the mineral-type particulate, there is the rough sledding of the dispersed variation that makes this mineral-type particulate in order to make patent documentation 1 such polypropylene-based resin film.
In addition,, developed by utilization and had the particle diameter of the size set and the mineral-type particulate of apparent specific gravity, the technology (patent documentation 2) that the dispersiveness that adopts the mineral-type particulate in the polypropylene-based resin that vapor phase method obtains is improved in order to eliminate this rough sledding.
Patent documentation 2: the spy opens flat 8-81591 communique
Summary of the invention
But, in the method for patent documentation 2, the mineral-type particulate that can utilize be limited to have bigger particle diameter, apparent specific gravity is big, pore volume is little mineral-type particulate.Therefore, may not necessarily obtain the polypropylene-based resin film of adhesion inhibiting properties excellence, can not make it embody good sliding, wrinkling on the film volume easily when therefore film being coiled into web-like.In addition, if use wrinkling like this film to involve in capable bag processing or printing processing, disqualification rate can improve.
The objective of the invention is to eliminate the problem in the above-mentioned film of polypropylene-based resin in the past, the polypropylene-based resin film is provided, it is by adopting vapor phase method low price, the efficient polypropylene-based resin of making to form, the adhesion inhibiting properties excellence, sliding is good, do not crease easily on the film volume when coiling into web-like, it is good that bag adds man-hour, printing adds the processability in man-hour.In addition, providing can be at a low price and efficiently make the manufacture method of this polypropylene-based resin film.
In the present invention, the present invention 1 formation relates to polypropylene resin laminated film, this polypropylene resin laminated film is at the laminated sealant that has based on polyolefin resin of tow sides based on the basic unit of polypropylene-based resin, thickness is that 10 μ m are above, less than 70 μ m, and haze value is more than 0.4%, below 5.0%, wherein: the polypropylene-based resin that constitutes basic unit and sealant adopts vapor phase method to form, and satisfies following formula (1), (2)
(1) coefficient of kinetic friction of measuring under 40 ℃ atmosphere (hereinafter referred to as μ H40) is more than 0.2, below 1.1,
(2) air exhaust index (hereinafter referred to as AR) is more than 1.8 seconds, below 10.0 seconds, this air exhaust index be with 2 film overlaies, when decompression until time from emptying air between the film.
The present invention 2 formation relates to: in the present invention 1, at least basic unit has been carried out biaxial tension.
The present invention 3 formation relates to: in the present invention 1, contain more than the 15mg/kg in the whole layer of laminate film, the Al of not enough 150mg/kg.
The present invention 4 formation relates to: in the present invention 1, basic unit is formed by propylene-ethylene copolymers, and ethylene contents is that 0.5 weight % is above, less than 1.5 weight % in this propylene-ethylene copolymers.
The present invention 5 formation relates to: in the present invention 1, sealant is 1/60~1/3 with respect to the ratio of whole layers thickness of laminate film.
The present invention 6 formation relates to: in the present invention 1, be added with anti-clouding agent in basic unit and sealant.
The present invention 7 formation relates to: in the present invention 6, be equipped with in covering under the state of peristome of container of 50 ℃ of warm water, the bond area of the dew after taking out under the atmosphere in room temperature after placing 30 minutes under 5 ℃ the atmosphere be below 1/4 of integral body.
The present invention 8 formation relates to: in the present invention 1, use is adjusted to the point of a knife angle 60 degree, the point of a knife design temperature is adjusted to 390 ℃ fusing sealer, and the disqualification rate when making the fusing sealing bag of film with 120 bags/minute jet velocity under 370 ℃ of point of a knife temperature is below 5%.
The present invention 9 formation relates to: in the present invention 1, at 140 ℃ down with adding 1kg/cm in 1 second
2Pressure make between the sealant heat fusing bonding after, the intensity when peeling off these heat fusing bonding portions with 180 degree is more than the 1.5N/15mm, below the 6.0N/15mm.
The present invention 10 formation relates to: in the present invention 1, the wetting tension on sealant surface is more than the 35mN/m, below the 45mN/m.
The present invention 11 formation relates to: in the present invention 1, the resin that forms sealant is melt flow rate (MFR) to be adjusted to 1.5g/10 divide resin above, that 9.0g/10 divides or their mixture.
The present invention 12 formation relates to: in the present invention 1, be added with more than the average grain diameter 1.0 μ m in forming the polyolefin type resin layer of sealant, less than 12.0 μ m, pore volume is that 1.0ml/g is above, the mineral-type particulate of not enough 2.0ml/g.
The present invention 13 formation relates to: in the present invention 6, anti-clouding agent and with in polyoxyethylene alkyl amine type anti-clouding agent, polyoxyethylene alkyl amine fatty acid ester type anti-clouding agent, the fatty glyceride type anti-clouding agent more than at least 2 kinds.
The present invention 14 formation relates to: in the present invention 6, the anti-corona dosage in whole layers of laminate film is that 0.2 weight % is above, less than 1.5 weight %.
The present invention 15 formation relates to the manufacture method that is used to make the present invention's 1 described polypropylene resin laminated film, it comprises: by adopt coetrusion from a plurality of extruders polypropylene-based resin and polyolefin resin are melt extruded, form polypropylene resin laminated filming operation that does not stretch and not stretching of will in this filming operation, obtaining the polypropylene resin laminated longitudinally and laterally biaxial tension operation of biaxial tension; Satisfy following important document (a)~(c):
(a) above-mentioned filming operation is adopt to add the propylene-ethylene copolymers of mineral-type particulate and granulation 1 time, add the propylene-ethylene copolymers of mineral-type particulate and granulation 2 times, the operation that polypropylene-based resin forms sealant,
(b) above-mentioned filming operation is to adopt propylene-ethylene copolymers to form basic unit, simultaneously the ethylene contents in this propylene-ethylene copolymers is adjusted to that 0.5 weight % is above, less than 1.5 weight %,
(c) above-mentioned biaxial tension operation is longitudinally and laterally to carry out heat fixation after the biaxial tension, with the adjustment of above-mentioned heat fixation is simultaneously more than 160 ℃, 170 ℃ of less thaies.
The present invention 16 formation relates to: in the present invention 15, the rotary body that employing is rotated with the rotary speed more than the 100rpm, below the 500rpm carries out the granulation in the above-mentioned filming operation.
The present invention 17 formation relates to polypropylene resin laminated film, this polypropylene resin laminated film is at the laminated sealant that has based on polyolefin resin of tow sides based on the basic unit of polypropylene-based resin, thickness is that 10 μ m are above, less than 70 μ m, and haze value is more than 0.4%, below 5.0%; The polypropylene-based resin that constitutes basic unit and sealant adopts vapor phase method to form, form with resin laminated by in the T pattern, making the basic unit that melt extrudes by the 1st extruder form the sealant that melt extrudes with resin, by the 2nd extruder simultaneously, making is basic unit and the laminated laminated resin sheet that does not stretch of the sealant narrower than this base width, laminated biaxial tension of resin of the not stretching that will make then and forming; Satisfy following formula (1), (2):
(1) coefficient of kinetic friction of measuring under 40 ℃ atmosphere is more than 0.2, below 1.1,
(2) air exhaust index is more than 1.8 seconds, below 10.0 seconds, this air exhaust index be with 2 film overlaies, when decompression until time from emptying air between the film.
The present invention 18 formation relates to: in the present invention 17, as above-mentioned T pattern, utilize sealant form with resin pass through partly about two ora terminalis the T pattern of pad is installed.
Polypropylene resin laminated film of the present invention can utilize the polypropylene-based resin manufacturing of adopting vapor phase method to make, therefore can be at a low price, make efficiently.In addition, the adhesion inhibiting properties excellence, sliding is good, does not crease easily on the film volume when coiling into web-like, and it is good that bag adds man-hour, printing adds the processability in man-hour.In addition, because the anti-clouding agent that is added is difficult for separating out from the teeth outwards therefore anti-corona property excellence, and transparency excellence.Therefore, polypropylene resin laminated film of the present invention is applicable to the packing purposes of raw and fresh foods such as vegetables.
On the other hand, adopt the manufacture method of polypropylene resin laminated film of the present invention, as mentioned above, can be at a low price and make efficiently that anti-corona property excellence, the transparency are high, bag adds man-hour or printing adds the good polypropylene resin laminated film of processability in man-hour.
Description of drawings
Fig. 1 is the key diagram in the cross section of the device of the air exhaust velocity of expression mensuration film.
The key diagram in the cross section that the resin that Fig. 2 does not stretch for expression is laminated.
Symbol description
1: platform dish, 2,8: thin film platen, 2a: ditch hole, 2c: hole, 2d: pore, 3: bolt, 4,5: film, 6: vavuum pump, 7: valve, X: film overlay part.
The specific embodiment
In polypropylene resin laminated film of the present invention, as being mainly used in the polypropylene-based resin that forms basic unit, can enumerate use by the catalyst that becomes to be grouped into as solid catalyst component, organo-aluminum compound composition and electron donability compound that must composition with aluminium, magnesium, titanium and halogen, carry out the resulting polypropylene-based resin of gas-phase polymerization under the liquid medium not existing basically.
In addition, polyolefin resin as the sealant that is suitable for forming polypropylene resin laminated film of the present invention (hot sealing layer), comprise polyolefin resin, can use for example ethene-1-Butylene copolymer with fusing point lower than the polypropylene-based resin that forms basic unit, ethylene-propylene-1-Butylene copolymer, ethylene-acrylic acid copolymer, by the metal ion ionomer that ethylene-acrylic acid copolymer is crosslinked, polypropylene, PB Polybutene-1, butylene-ethylene copolymer, propylene-ethylene copolymers, propene-1-butene-1 copolymer, propylene-ethylene-butene-1 copolymer, more than a kind or 2 kinds of propylene pentene-1 copolymer etc.The random copolymer of wherein preferred propylene and ethene and the alpha-olefin of carbon number more than 4, for making fusing point reach compounding below 140 ℃, but in the scope of the characteristic of not destroying film, also can use polyester resin, polyamide-based resin, polycarbonate resin etc.In addition, also at random compounding ultra-violet absorber, antioxidant, antistatic additive etc.In addition,, consider economy as the polymerization of resin, can enumerate with basic unit in the resin that uses adopt the method for gas-phase polymerization like that.
The sealant surface of polypropylene resin laminated film of the present invention must have anti-corona property.Promptly, as polypropylene resin laminated film of the present invention, be used to pack under the situation of film of purposes, thereby the turbid phenomenon that not only prevents the package body inner face improves commodity value, even aspect the aqueous corrosion of the content of the package body that prevents to cause owing to water droplet that muddy carrying out forms, anti-corona property also is extremely important characteristic.As making sealant surface embody the method for anti-corona property like that, suitable use during preservation, circulation period makes and the method for (separating out) anti-clouding agent appears in the join sealant surface of side of raw and fresh food.In addition, make the sealant surface separate out anti-clouding agent for like that during preservation, in the circulation period, can adopt when thin film fabrication when melt extruding (material resin) at the resin that forms basic unit, form the method for at least one side's compounding anti-clouding agent of the resin of sealant.If adopt as mentioned above when the melt extruding of material resin in basic unit and form the method that resin, sealant form compounding anti-clouding agent in the resin, with compare in the method for the surface of film coating anti-clouding agent, can stably continue to bring into play anti-corona property at circulation period with the changes in temperature temperature Change.
In addition, when adopting, form resin in basic unit in the melt extruding of material resin, when sealant forms the method for compounding anti-clouding agent in the resin, if form compounding anti-clouding agent in resin and the sealant formation resin in basic unit, because separating out continuously of anti-clouding agent is preferred for a long time and not.Moreover, even only form under the situation of compounding anti-clouding agent in the resin in basic unit and since basic unit form in the resin anti-clouding agent during preservation, separate out on the sealant surface successively by sealant in the circulation period, so the sealant surface has anti-corona property gradually.In addition, for excellent anti-corona property is continued chronically, must become following state: even the muddiness that produces owing to the effect of the content that prevents package body flows out the anti-clouding agent on surface, inner anti-clouding agent also can in time and constantly be separated out on the sealant surface successively, and the sealant surface has anti-corona property.Therefore, when the anti-corona characteristic among setting the present invention, preferably consider the appearance property again after surperficial anti-clouding agent is wiped away.
As the anti-clouding agent that uses among the present invention, preferably with polyoxyethylene alkyl amine type, polyoxyethylene alkyl amine fatty acid ester type, fatty glyceride type and usefulness, as the polyoxyethylene alkyl amine type, can enumerate polyoxyethylene lauryl amine, polyoxyethylene tallow amine, polyoxyethylene stearyl amine, polyoxyethylene oil base amine, polyoxyethylene tallow propane diamine, polyoxyethylene stearyl base propane diamine, polyoxyethylene N-cyclohexylamine, polyoxyethylene m-xylene diamine.In addition, as the typical example of polyoxyethylene alkyl amine fatty acid ester type, can enumerate typical example and the following aliphatic acid that illustrates and the anti-clouding agent that carries out the ester bond combination of above-mentioned polyoxyethylene alkyl amine type.As aliphatic acid, can enumerate stearic acid, mountain Yu's acid, laurate, oleic acid, palmitic acid, coconut fatty acid, tallow fatty acids, vegetable seed aliphatic acid, castor-oil plant aliphatic acid, myristic acid.In addition, as fatty glyceride, can enumerate myristic acid monoglyceride, monostearate monoglyceride, single isostearic acid monoglyceride, single monoolein, single olive oil monoglyceride, two monooleins, distearyl acid monoglyceride, single undecenoic acid monoglyceride etc.
In addition, except above-mentioned 3 kinds of anti-clouding agents, can add other anti-clouding agent, as such anti-clouding agent, can enumerate with monostearate two glyceride, single isostearic acid two glyceride, single oleic acid two glyceride, two oleic acid, two glyceride, three isostearic acids, two glyceride etc. is polyglyceryl fatty acid ester type of representative etc.
Bring into play anti-corona property and preferred anti-corona dosage as being used among the present invention, the inner and outside total of film, preferred anti-clouding agent exists with the scope of 0.2~1.5 weight %, more preferably 0.3~1.2 weight %, the more preferably scope of 0.5~1.0 weight %.If the quantity not sufficient of anti-clouding agent 0.2 weight %, owing to can not bring into play sufficient anti-corona effect, therefore not preferred, if the amount of opposite anti-clouding agent surpasses 1.5 weight %, the anti-clouding agent state that reaches capacity, not preferred economically, and a large amount of anti-clouding agents is transferred to film surface, film surface becomes the state that dusts, and makes degraded appearance, and is therefore not preferred.
On the other hand, in order to improve adhesion inhibiting properties, to improve sliding, must in the resin that forms sealant, add the mineral-type particulate.As this mineral-type particulate, can use average grain diameter is 1.0~12.0 μ m, preferred 1.3~4.0 μ m, and pore volume is the mineral-type particulate of 1.0~2.0ml/g, preferred 1.25~1.80ml/g.If any one of average grain diameter, pore volume outside this scope, then can not obtain good adhesion inhibiting properties, sliding.That is, if average grain diameter less than 1.0 μ m, the adhesion inhibiting properties deficiency of film then, and be difficult to μ H40 is adjusted in 0.2~1.1 the scope, therefore not preferred, if the opposite 12.0 μ m that surpass, outward appearance, transparency deterioration and not preferred.In addition, if pore volume surpasses 2.0ml/g, the dispersion variation with resin when mixing, if not enough 1.0ml/g, except scratch resistance worsened, the population that unit adds weight tailed off, the result must increase addition when adding the number of particles of equivalent, makes transparent variation, and is therefore not preferred.The mineral-type particulate preferably uses silica, magnesium silicate, alumina silicate, calcium carbonate, magnesia etc.In these mineral-type particulates, especially preferably use the silica of average grain diameter 1.5~4.0 μ m, pore volume 1.0~2.0ml/g.In addition, the mineral-type particulate is preferably 0.05~0.60 weight portion with respect to the compounding amount of the resin that forms basic unit, sealant with respect to resin 100 weight portions.If less than 0.05 weight portion, the adhesion inhibiting properties deficiency, if surpass 0.60 weight portion, then dispersed the deterioration causes the deterioration of outward appearance, the transparency, and be therefore not preferred.From adhesion inhibiting properties and dispersed aspect, the compounding amount of mineral-type particulate is 0.10~0.40 weight portion more preferably.Especially preferably use the silica of compounding amount 0.10~0.40 weight portion, average grain diameter 1.5~4.0 μ m, pore volume 1.0~2.0ml/g.Moreover the pore volume of mineral-type particulate can adopt based on the known method such as method of the JIS-K-1150 of BET mode and measure.In addition, as the determinator of pore volume, suitable カ Application Network ロ one system society system just a ト ソ one Block 1, Shimadzu Seisakusho Ltd.'s system high speed specific area/pore measure of spread device ア サ ッ プ 2400 etc. of using.
In addition, the haze value of polypropylene resin laminated film of the present invention must be adjusted to 0.4%~5.0% by content in order to recognize easily.If it is not haze value surpasses 5.0%,, therefore preferred because the transparency becomes not enough when being used for the packing purposes of raw and fresh food.In addition, the lower limit of haze value is preferably more than 0.8%, is preferably more than 1.0% especially.In addition, the upper limit of haze value is preferably below 4.0%, is preferably below 3.5% especially.Moreover preferred haze value is low more good more, but considers that adding anti-blocking agent in resin is must be obligato, therefore thinks that the polypropylene-based resin film that will obtain haze value less than 0.4% comes down to impossible.
In addition, polypropylene resin laminated film of the present invention preferably in the whole layer of laminate film, contain more than the 15mg/kg, the Al of not enough 150mg/kg.Usually in polyacrylic polymerization, use organo-aluminum compound as co-catalyst, in polymerizations in the past such as solvent method, the operation of removing by catalyst is removed organo-aluminum compound, and in the pp material that the gas phase polymerization that uses in adopting the present invention obtains, only carry out the inactivation of catalyst, therefore in raw material, have Al.That is the laminate film that in laminate film, exists Al to mean to be to use the pp material that adopts gas phase polymerization to obtain to make.The pp material that adopts gas phase polymerization to obtain is compared with the pp material that adopts the solvent method raw material to obtain, since do not need catalyst, atactic polypropylene the removal operation, it removes necessary solvent recovery operation, therefore be economic raw material aspect energy consumption, use the laminate film of this raw material manufacturing also to can be described as the film pollution-free, economic earth environment.In addition, the content of preferred Al with respect to the whole layer of laminate film be more than the 20mg/kg, not enough 80mg/kg.Moreover, laminate film all in the layer amount of contained Al can adopt and ormal weight (about 1.0g) dry type decomposed and try to achieve with employing plasma luminescence analysis carrying out method for measuring after the acid treatment etc.
In addition, the resin of the formation sealant of polypropylene resin laminated film of the present invention preferably is adjusted to melt flow rate (MFR) 1.5g/10 and divides resin above, that 9.0g/10 divides or their mixture.Form as sealant and use resin by will be like this having carried out the resin regulated or their mixture, adopt the coefficient of kinetic friction (μ H40) of the film that granulation described later carries out, the adjusting of AR value to become easy melt flow rate (MFR).
In addition, when the polypropylene-based resin film is made and batch to the material volume continuously, stablize the time that is starved of (in common about 40 ℃ following time of atmosphere, the labile state of rerum natura continued about 12 hours) until rerum natura.In addition because the rerum natura of the film after making like this is unstable for a long time, therefore since produce batch tightly puckery, wrinkling easily on the film volume.
Inventors of the present invention etc. are according to above-mentioned experience, on the film volume, do not crease easily in aging in order to make, infer that it is not enough only controlling coefficient of friction as it has been generally acknowledged that, satisfy between the film that batches (surface of film and the back side) slip and be must be obligato moderately mutually simultaneously from the speed discharge air with appropriateness between the film that batches.Infer that in addition the sliding condition between the film batch whether can be by the coefficient of kinetic friction (the be μ H40) estimation of the stable film of rerum natura (film after aging) 40 ℃ under, estimate from the value of AR (air exhaust index) whether the easy degree of the discharge air between the film that batches can be by the stable film of rerum natura.In addition, based on these inference, the μ H40 of the stable film of the wrinkling degree in aging and rerum natura and the relation of AR value have been carried out conscientiously studying, found that: in the stable film of rerum natura, when μ H40 and AR value within the limits prescribed the time, on the film volume, do not produce fold in aging.But, for the film that as polypropylene resin laminated film of the present invention, requires low haze valus (being high transparent), the kind of the antiseize paste that adds, amount are restricted significantly, so kind, the amount of only merely regulating antiseize paste, μ H40 and AR value can not be controlled at desired scope, the control of the degree of scatter of antiseize paste in resin also is necessary.In addition, present inventors etc. are considering to have carried out trial and error test (repetition test) in the degree of scatter of antiseize paste in resin, found that the method described later (with reference to 0053 paragraph-0064 paragraph) that adopts, under the situation of not using a large amount of antiseize pastes, can access the polypropylene-based resin film that satisfies desired haze value, desired μ H40, desired AR value simultaneously, thereby finish the present invention.
That is, the coefficient of kinetic friction (being μ H40) measured under 40 ℃ atmosphere of polypropylene resin laminated film of the present invention is necessary for 0.2~1.1.If μ H40 is then sliding excessively between the film less than 0.2, batch to producing behind the web-like and batch dislocation, therefore not preferred, if opposite μ H40 surpasses 1.1, then sliding is poor, batches to wrinkling easily on the film volume, therefore not preferred behind the web-like.Moreover the lower limit of μ H40 is preferably more than 0.3, is preferably more than 0.35 especially.In addition, the upper limit of μ H40 is preferably below 1.0, is preferably below 0.95 especially.
In addition, polypropylene resin laminated film of the present invention with 2 film overlaies decompression the time, as be necessary for 1.8 seconds until air exhaust index (being AR) from time of emptying air between film~10.0 seconds.Polypropylene resin laminated film is batched when rolling up as film for web-like, and preferred limit is involved in the air in certain amount limit and batches.If the amount of being involved in is few, not only adhesion easily, and under the situation of as the present invention polypropylene resin laminated film, because its glass transition temperature is in sub-zero scope, even also can cause change in size at normal temperature, cause change in size owing to following between the film that overlaps, produce fold, so not preferred.Particularly for oriented film, residual when stretching have the direction of stress wrinkling easily.On the other hand, if the air that is involved in is too much, the film of coincidence is distortion freely separately, therefore produces to relax on film, produces fold on the direction vertical with film flow direction (take-up direction), and is therefore not preferred.In addition, if the AR value is lower than 1.8 seconds, since the very fast disappearance of air that is involved in, adhesion between the film, and the residual stress during stretching goes up goods film volume and produces fold, therefore not preferred, if opposite AR value greater than 10.0 seconds, because the air that is involved in is forever kept, therefore produces lax on film, on direction vertical on the goods film volume, produce fold with the film flow direction, therefore not preferred.Moreover the lower limit of AR value was preferably more than 2.0 seconds, was preferably especially more than 2.5 seconds.In addition, be limited on the AR value below 9.0 seconds, be preferably especially below 8.0 seconds.
In addition, polypropylene resin laminated film of the present invention under 140 ℃, add 1 second 1kg/m
2Pressure make between the sealant heat fusing bonding after, the intensity (so-called sealing intensity) when these heat fusing bonding portions 180 degree are peeled off be preferably 1.5N/15mm above, less than 6.0N/15mm.If the not enough 1.5N/15mm of sealing intensity, bag too easily is opened when being used to pack purposes, and is therefore not preferred, if opposite sealing intensity is more than the 6.0N/15mm, bag is difficult for being opened when being used to pack purposes, and is therefore not preferred.Moreover the lower limit of sealing intensity is preferably more than the 2.0N/15mm, is preferably more than the 3.0N/15mm especially.In addition, the upper limit of sealing intensity is preferably less than 5.0N/15mm, is preferably less than 4.0N/15mm especially.
On the other hand, the viewpoint of the manifesting property of the anti-corona effect that produces from printing and anti-clouding agent, the wetting tension on the sealant surface of polypropylene resin laminated film of the present invention must be adjusted to 35mN/m above, below the 45mN/m.In addition, the lower limit of the wetting tension on sealant surface is preferably more than the 37mN/m, and the upper limit of the wetting tension on opposite sealant surface is more preferably below the 43mN/m.If the not enough 35mN/m of wetting tension, the manifesting property of the anti-corona effect of film surface becomes bad, and is therefore not preferred, if opposite wetting tension greater than 45mN/m, then is easy to generate adhesion, wall is bad, and is therefore not preferred.
Below the preferable production process of polypropylene resin laminated film of the present invention is described.Non-stretched film is preferably as follows formation: will form based on the basic unit of crystalline polypropylene with resin with based on the sealant formation of polyolefin and supply with extruder respectively with resin, be heated fusion, by behind the filter, in the T pattern, basic unit formed under 220~320 ℃ the temperature form with resin and sealant with resin laminated after, T pattern outlet by slit-shaped melt extrudes, and forms continuous non-stretched film by making its cooling curing.At this moment, if resin is dropped on the hauling machine (carry-over pinch rolls) of rotary drum shape, blow with air knife from the face of the opposition side of the face that contacts with carry-over pinch rolls, the adaptation of stretched sheet and carry-over pinch rolls increases, obtain surface smoothing, thickness stretched sheet not uniformly, therefore preferred.This moment, the blast of air knife was preferably 700~2200mmH
2The scope of O.If blast is low, the driving fit of stretched sheet and carry-over pinch rolls does not become inhomogeneous, and is therefore not preferred, if opposite blast height at stretched sheet not, becomes inhomogeneous with the driving fit of carry-over pinch rolls, therefore not preferred.In addition, the resin temperature when melt extruding as mentioned above is preferably the temperature range that does not produce the resin degraded, is the temperature range about 230~290 ℃, more preferably the temperature range about 270~280 ℃.
In addition, form with resin based on the basic unit of crystalline polypropylene when melt extruding and form the resin temperature of usefulness resin based on the sealant of polyolefin, when there is clear and definite fusing point separately in resin, be preferably than the high temperature more than 60 ℃ of its fusing point, more preferably high more than 70 ℃ and be unlikely to the temperature of thermal degradation.If resin temperature in such temperature range, can reduce the influence that the relaxation time of the melting deformation of the molecular weight distribution that depends on polyolefin resin when melt extruding distributes, therefore can reduce the in uneven thickness of non-stretched film.In addition, the carry-over pinch rolls temperature preferably is adjusted to the temperature below 30 ℃, more preferably is adjusted to below 20 ℃.If the resin temperature when melt extruding is low, carry-over pinch rolls temperature height, then the crystallization of resin carries out easily, and film surface becomes shaggy state, is easy to generate in uneven thickness, therefore not preferred.
After forming non-stretched film as mentioned above,, this non-stretched film makes its double orientation by being carried out biaxial tension.As drawing process, can use one by one bidirectional extending method or while bidirectional extending method.As bidirectional extending method one by one, can adopt the temperature that non-stretched film is heated to 90~140 ℃, after 3~7 times of length direction stretchings, cool off, import then in the expanding formula stretching-machine, be heated to 130~175 ℃ temperature, after 7~12 times of width stretchings, under the temperature of setting, carry out heat fixation (heat treatment), make width relax 2~15%, preferred 4~10%, the method for batching after the cooling.Carry out heat fixation by relax the limit like this in the stretching back, the deformation of melting deformation that depends on the molecular weight distribution of polyolefin resin is eliminated, the rerum naturas such as heat-shrinkable of laminate film are stable on the whole width of film, the contraction of the sealing when its result can obtain sealing, change in size reduce, so that the good package body of the distortion of no sealing.Should illustrate, to preferred heat fixation method with aftermentioned.
The ratio of the thickness of laminated sealant is not particularly limited in basic unit, but common whole layers (basic unit and sealant) with respect to laminate film, be preferably 1/60~1/3 (its gross thickness when the laminated sealant in the two sides of basic unit), more preferably 1/50~1/5, be preferably 1/30~1/10 especially.If the thickness ratio of sealant is littler than 1/60, bag adds the sealing intensity deficiency in man-hour, and package body lacks reliability, and is therefore not preferred.In addition, the thickness ratio of sealant is greater than 1/3 o'clock, and the ratio of basic unit's part is little, thus laminate film on the whole so-called " waist " do not exist, fill the shape instability of the package body behind the content, do not have commodity value, therefore not preferred.In addition, the thickness of laminate film is not particularly limited, and as the packaging film with high anti-corona property, can suitably determine in the scope about preferred 10~70 μ m.Moreover the scope of the preferred thickness of laminate film is 15~60 μ m.
In addition, polypropylene resin laminated film of the present invention is mainly used in the purposes of fresh food condiment products such as packing vegetables, therefore preferably has good fusing sealing.Particularly, use with the point of a knife angle be adjusted to 60 degree, the point of a knife design temperature is 390 ℃ a fusing sealer, when making the fusing sealing bag of film with 120 bags/minute jet velocity under 370 ℃ of point of a knife temperature (actual temperature of point of a knife), the disqualification rate of per 1000 the fusing sealing bags that are preferably formed (having produced the ratio of rough sledding at molten condition and dissengaged positions) is below 5%.In addition, disqualification rate more preferably below 4%, more preferably below 3%, more preferably below 2%, is preferably below 4% especially.
In addition, polypropylene resin laminated film of the present invention can be implemented surface treatments such as Corona discharge Treatment, flame treatment on a surface or two surfaces.Should illustrate, for the method for preferred Corona discharge Treatment with aftermentioned.
In addition, in order to obtain polypropylene resin laminated film of the present invention, must adopt the means of following (1)~(4) during fabrication.By adopting this means, it is good to obtain anti-corona property, the transparency, adhesion inhibiting properties, sliding, the film that does not crease easily when batching to web-like.In addition, by adopting the means of following (5), can stably make long film.
(1) sealant forms the adjusting of the dispersion condition of the mineral-type particulate in the resin
(2) basic unit forms the adjusting of ethylene contents in the resin
(3) adjusting of the heat fixation condition behind the cross directional stretch
(4) adjusting of Corona discharge Treatment condition
(5) adjusting of the shape of laminated resin sheet
Below each above-mentioned means are described successively.
(1) sealant forms the adjusting of the dispersion condition of the mineral-type particulate in the resin
In the manufacturing of polypropylene resin laminated film of the present invention, when in the polypropylene-based resin that forms sealant, adding the mineral-type particulate, not that the mineral-type particulate that adds powder in extruder carries out mixing, in polyolefin resin, add the mineral-type particulate of high concentration and make the masterbatch polymer chips, the method for diluting and must adopt in advance with not containing this masterbatch of polyolefin resin blend of mineral-type particulate.
In addition, form the masterbatch section of sealant, must in polyolefin resin, add the mineral-type particulate, after stirrings such as mixer, blender, this mixture is dropped in the extruder, carry out mixing, melt extrude and after forming graininess, mix with the section of the polyolefin resin that does not contain the mineral-type particulate and utilize (following with in resin, add the mineral-type particulate as mentioned above, stir the back drop into carry out in the extruder mixing, melt extrude and form granular operation and be called granulating working procedure).
In addition, as the masterbatch section that forms sealant, must and usefulness only implemented the section (1 granulation section) of 1 mixing operation and repeatedly the section of 2 mixing operations (2 granulations section).In addition, with 1 granulation section and 2 granulations section and time spent, the mixing ratio that 1 granulation section and 2 granulations are cut into slices preferably is adjusted in 1: 9~9: 1 the scope when like this.In addition, when 1 granulation section and 2 granulations are cut into slices the also time spent, the particle diameter of the mineral-type particulate that adds when formation is cut into slices in the particle diameter of the mineral-type particulate that adds when 1 granulation section is formed and 2 granulations is approaching as far as possible.That is, with 1 granulation section and 2 granulations section and time spent, the difference of the particle diameter of the mineral-type particulate that adds when the particle diameter of the mineral-type particulate that adds when 1 granulation section is formed and 2 granulations section form is less than 2.0 μ m.
When sealant formed, if only use 2 granulations section of having added less than the mineral-type particulate of the small particle diameter of 1.5 μ m, then μ H40 increased, and sliding worsens, and is easy to generate fold when batching to web-like on the film volume, and is therefore not preferred.Moreover, if on film volume, produce fold as mentioned above, then batch during the keeping of film volume tightly puckeryly, the air that is involved between film reduces, so anti-clouding agent is difficult for separating out the anti-corona property deterioration of film.In addition, if film volume produces fold, during fusing bag processing (lamination process), can not attractive in appearance ground bag, formation bag degraded appearance.In addition, if only use 1 granulation section of the mineral-type particulate that has added the big particle diameter more than the 1.5 μ m, the AR value extremely diminishes, and the above-mentioned air that is involved between film equally reduces, therefore follow between the film that when the keeping of film volume, overlaps and be out of shape, on the film volume, be easy to generate fold, therefore not preferred.In addition, with above-mentioned same, anti-clouding agent is difficult for separating out, the anti-corona property variation of film.In addition,,, on film, form flake and make bad order because the mineral-type particulate is dispersed not enough if only use 1 granulation section added less than the mineral-type particulate of the small particle diameter of 1.5 μ m, therefore not preferred.In addition, as the masterbatch section that forms sealant, except 1 granulation section and 2 granulations section of having added inorganic particulate, in the scope that does not make fusing sealing intensity variation, also can will add the granulation section of organic based fine particles and use.
In addition, carry out as mentioned above when mixing, preferably the rotary speed with the rotary bodies such as screw rod of extruder is adjusted to 100rpm~500rpm, more preferably is adjusted to 250rpm~450rpm, especially preferably is adjusted to 270rpm~430rpm.In addition, when 2 granulations as mentioned above, the rotary speed height of the rotary body of the rotary speed of the rotary body when preferably making the 1st granulation during than the 2nd granulation.
(2) basic unit forms the adjusting of ethylene contents in the resin
In the manufacturing of polypropylene resin laminated film of the present invention, as mentioned above, the polypropylene-based resin as forming basic unit can use with the various polypropylene-based resins of polypropylene as principal component, wherein, preferably utilize resin or its modifier of polypropylene and ethylene copolymer.In addition, in this copolymer, modifier, the containing ratio that preferably uses ethene be 0.5 weight % above, less than the resin of 1.5 weight %.By using this resin, the anti-clouding agent that adds in basic unit is separated out easily, and the anti-corona property of polypropylene-based resin film (anti-corona property of initial stage described later and anti-corona continuation) further improves.
If the ethylene contents in the copolymer of formation basic unit is more than the 1.5 weight %, film softens and is difficult for sliding, and μ H40 increases.In addition, the AR value increases, and is difficult for discharging air between the film that batches, and is wrinkling easily on the film volume.In addition, it is thermo-labile that film becomes, and haze value increases, and the transparency reduces.If opposite ethene contain quantity not sufficient 0.5 weight %, anti-clouding agent becomes and is difficult for separating out, can not obtain good anti-corona property, and melting adhered part loses viscosity, produce the shape deterioration of melting adhered part, can not obtain good sealing intensity, bag adds the fusing sealing variation in man-hour, and is therefore not preferred.
(3) adjusting of the heat fixation condition behind the cross directional stretch
In addition, polypropylene resin laminated film of the present invention, as mentioned above, with the non-stretched film that adopts coetrusion to form at laminated sealant in the basic unit along length and width two after stretching, carry out heat fixation and make.In the manufacturing of this biaxially oriented film, when the manufacturing of common polypropylene-based resin film, usually be lower than more than 155 ℃ of fusing point slightly, carrying out heat fixation under less than 160 ℃ temperature conditions, but, must under temperature quite high usually more than 160 ℃, less than 170 ℃ ratios, carry out heat fixation and handle in order to obtain film of the present invention.Handle by carry out heat fixation under high like this temperature, the shrinkage stress of film is removed, batch for behind the web-like through the time change and be inhibited, the generation of fold is lowered to quite low level.In addition, it is bad can not produce separating out of anti-clouding agent that the generation of fold causes, can not produce the situation of the anti-corona property variation of film.In addition, also can not produce the variation of processability in bag processing that the generation of fold causes, the printing processing.
If the temperature that heat fixation is handled surpasses 170 ℃, though film surface fusing produces thermo-labile, rough surface, μ H40 descends, and becomes easily to slide the easy exhaust (AR diminishes) that becomes of the air between film, but the transparency of film, outward appearance become bad, become not to be durable and not preferred.If the temperature that opposite heat fixation is handled is lower than 160 ℃, the slowly cooling that easily becomes, spherocrystal was grown up when the surface recrystallized, transparent variation, and the shrinkage stress of film increases, through the time change and increase, wrinkling easily on the film volume, therefore not preferred during keeping.
(4) adjusting of Corona discharge Treatment condition
In the manufacturing of polypropylene resin laminated film of the present invention, must under rated condition, implement Corona discharge Treatment in the surface to film.That is, Corona discharge Treatment can adopt known the whole bag of tricks, but preferably adopts the film surface after the electrode pair biaxial tensiones such as aluminum rod type that are suspended in the thin-film width direction to implement, preferably after the interval with film and electrode is adjusted to 1~3mm, at 15~45W/m
2Carry out under the processing power of/min.In addition, the wetting characteristics of the film surface behind the corona discharge must be adjusted to more than the 35mN/m, the scope of 45mN/m.
If a little less than the degree of Corona discharge Treatment, inner additives such as antiseize paste become and are difficult for precipitateing into the outside, sliding variation (μ H40 increases), and also air becomes and is difficult for exhaust (the value increase of AR).In addition, add man-hour at bag, the slip variation between two folding films, the friction of bag processing machine and film increases, and can not obtain the good fusing sealing bag of outward appearance sometimes.In addition, because inner anti-clouding agent also is difficult for precipitateing into the outside, therefore be difficult to show good anti-corona property.In addition, if the degree of Corona discharge Treatment is strengthened, the film surface coarse concave-convex surface of Corona discharge Treatment (formation result from), above-mentioned rough sledding is eliminated, sliding become well (μ H40 reduction), and the air easy exhaust (the AR value reduces) that becomes, if but the degree of Corona discharge Treatment extremely strengthens, the what is called of film surface " coarse " becomes serious, should " coarse " cause transparency decline (mist degree increase), and the speed of separating out of the anti-clouding agent that is added etc. becomes and is exceedingly fast owing to there is a large amount of anti-clouding agents, also sometimes through the time on (on the timeliness) cause the situation of transparent variation.In addition, the additive of film surface, resin degraded become lower-molecular substance, therefore become sticky easily, and easy adhesion becomes.At this moment, also peel off and make the decline of anti-corona property owing to one-sided anti-clouding agent sometimes when peeling off between the bonding film.Therefore, in order to manifest the sufficient anti-corona property and the transparency, manifest good fusing sealing, value with μ H40 and AR is controlled in the desired scope simultaneously, preferably carry out Corona discharge Treatment with the intensity of appropriateness, for this reason, it is effective implementing Corona discharge Treatment according to aforesaid way.
(5) adjusting of the shape of laminated resin sheet
In the manufacturing of polypropylene resin laminated film of the present invention, when utilizing coetrusion to form laminated resin sheet, must in the T pattern, make the basic unit that melt extrudes by the 1st extruder form with resin and by the sealant that the 2nd extruder melt extrudes form with resin laminated, fashionable in this molten resin layer, preferably by make sealant in the T pattern form with resin pass through partly narrowly than basic unit, go out interruption-forming with basic unit and the width sealant laminated laminated resin sheet narrower from the T pattern than this basic unit.As concrete means, preferably the sealant in the T pattern form usefulness resin pass through part about two ora terminalis installation pad, go out interruption-forming with basic unit and the width sealant laminated laminated resin sheet narrower from the T pattern than this basic unit.
If above-mentioned technology is elaborated, problem during as manufacturing goods volume, when laminated as laminated resin film of the present invention during low-melting resin in the film end of system during film, because the anchor clamps of the tentering machine when film and cross directional stretch are bonding, therefore produce sometimes stretch after from the tentering machine anchor clamps the such problem of film breaks during stripping film.When particularly making film at a high speed, it is remarkable that this problem is tended to become.In addition, when producing film continuously, the operations of implementing the part of tentering machine anchor clamps interlock is cut away, pulverizes, returned the raw material hopper of extruder more, at this moment, if occlusion portion is laminated low-melting raw material is arranged, it is bonding to produce this occlusion portion, is difficult to cutting, supplies to pulverizer, pulverizing, this occlusion portion becomes piece, problem such as can not supply with.In addition, will be fashionable in the T pattern by the resin bed that extruder is supplied with, pad (distance piece) is inserted at two ends at the T pattern, by making the low-melting-point resin that is laminated in superficial layer not be laminated to the both ends that become the occlusion portion of anchor clamps film, the generation of the problems referred to above can be reduced, the goods volume can be stablized, make continuously.
The assay method of the characteristic value that uses in this specification below is shown.
[40 ℃ the coefficient of kinetic friction (μ H40)]
Form below the film (mobile film) that is cut into prescribed level is wound up on the flat rectangular-shaped sectional fixture of 1500g of flat, make sealant become the outside, with the following (length * wide=7cm * 5cm) of mobile film covering sectional fixture.On the other hand, fit on the base station of level that a part (length is the part of 20cm) is heated to 40 ℃, make sealant upwards being cut into another film (fixed film) enough bigger than sectional fixture.Then, the sectional fixture that mobile film is installed is placed on the fixed film, the sealant of mobile film and the sealant of fixed film is engaged, under this state, utilize drive unit with the speed stretching sectional fixture that 2.5m/ divides, make from the heating part of base station and pass through.Then, with heating part by the time the coefficient of kinetic friction calculate as μ H40.Should illustrate that the film of measuring usefulness is aging more than 12 hours under 23 ℃, the atmosphere of 65RH%, mensuration itself is also carried out under 23 ℃, the atmosphere of 65RH%.In addition, mensuration is to change sample to carry out repeatedly 5 times, calculates its mean value as μ H40.
[air exhaust (gas leakage) index (Air Leakage:AR)]
The air exhaust velocity of film uses device shown in Figure 1 to measure.That is, film 4 is placed on the platform dish 1 of ring-type after, the thin film platen 2 with ring-type from the film 4 is placed on the platform dish 1, add under the state of tension force film 4 is fixing.Then, on thin film platen 2, place another film 5, place the thin film platen 8 of another ring-type again from this film 5, use bolt 3 that thin film platen 8,2 and platform dish 1 is fixing.Wherein, thin film platen 2 have circular ditch hole 2a in the above, hole 2c that the Outboard Sections of the part of this ditch hole 2a and thin film platen 2 is communicated with and pore 2d that the inside part of the part of ditch hole 2a and thin film platen 2 is communicated with.Should illustrate that 2 films 4,5 all are that the face that becomes the outside when batching to web-like becomes upside and is provided with.
After as mentioned above film being fixed, by making vavuum pump 6 work that are connected with pore 2c via valve 7, film 5 is adsorbed on the 2a of ditch hole, becomes the state that has added tension force.And then film 4 and film 5 overlapping film overlay part X also are depressurized via the pore 2d in the thin film platen 2, so film 4 and film 5 begin driving fit from peripheral part between its lap X.Closed state can be held by observing interference fringe from the top of film overlay part X.Then, after the periphery that is determined at film overlay part X produced interference fringe, interference fringe went up diffusion to whole of film overlay part X, until the time (second) that fringe movement stops, and should time (second) conduct " air exhaust index ".Should illustrate that mensuration is to change 2 film samples to carry out repeatedly 5 times, calculates its mean value as the AR value.
[haze value]
The Biaxially oriented film that obtains is cut into the size of regulation,, uses haze meter (Japanese electric look Industrial Co., Ltd system, 300A) to measure according to JIS K7136.Should illustrate that mensuration is to change sample to carry out repeatedly 5 times, obtains its mean value.
[anti-corona property of initial stage]
Anti-corona property by following sequential determination film.
(1) 50 ℃ warm water 300mL is packed in the upper opening container of 500mL.
(2) the anti-corona property mensuration face that makes film seals opening of container with film for inboard.
(3) after being placed in 5 ℃ the cold house, take out down, adhere to situation with the dew of following 6 grade evaluation films mensuration face in room temperature (about 23 ℃).Should illustrate that mensuration is to change film sample to carry out repeatedly 5 times, with its average grade as anti-corona property of initial stage (for example, each grade when measuring 5 times is 6,6,5,4,4 o'clock, is 5 grades).
[anti-corona continuation]
Anti-corona property by following sequential determination film.
(1) 50 ℃ warm water 300mL is packed in the upper opening container of 500mL.
(2) the anti-corona property mensuration face that makes film seals opening of container with film for inboard.
(3) be placed in 5 ℃ the cold house.
(4) in 5 ℃ cold house, place after 12 hours, transfer to 30 ℃ environment, placed 12 hours.
(5) with after the operation of carrying out (4) in 2 days repeatedly, the dew of measuring face with 6 following grade evaluation films adheres to situation.Should illustrate that mensuration is to change sample to carry out repeatedly 5 times, with its average grade as anti-corona continuation (for example, each grade when measuring 5 times is 6,6,5,4,4 o'clock, is 5 grades).
[fusing sealing]
Use fusing sealer (common prosperity printing machinery material (strain) system: PP500 type, SideWelder), make the fusing sealing bag (200mm * 300mm) of film under the following conditions.Then, obtain making per 1000 fusing sealing bags disqualification rate as fusing sealing.
Condition: fusing cutter: point of a knife angle 60 degree, 390 ℃ of point of a knife design temperatures, 370 ℃ of point of a knife actual temperatures; Jet number: 120 bags/minute
[heat seal strength]
Goods reeling width * length direction 500mm sample is taken a sample, with it at width 3 five equilibriums, choose the sample of width 50mm * length direction 250mm size from middle body separately, sealing surface is lumped together this sample doubling, at 140 ℃ of heat-sealing temperatures, pressure 1kg/cm
2, 1 second heat-sealing time condition under carry out hot plate sealing, make the wide test film of 15mm.Measure this test film 180 the degree peel strengths, with it as heat seal strength (N/15mm).Should illustrate that mensuration is to change the biaxially oriented film sample to carry out repeatedly 5 times, calculates its mean value.
[wetting tension]
According to the JIS-K-6768 method, under 23 ℃, the atmosphere of 65%RH, measure.Should illustrate that mensuration is to change the biaxially oriented film sample to carry out repeatedly 5 times, calculates its mean value.
[melt flow rate (MFR) (MFR)]
According to JIS K7210, the method for employing condition-14 is measured.Should illustrate that mensuration is to change the material resin sample to carry out repeatedly 5 times, calculates its mean value.
[ethylene contents]
Ethylene contents in the propylene-ethylene copolymers is to adopt macromolecule to analyze the method for the 615th~617 page of record of handbook (nineteen ninety-five, the distribution of Kinokuniya bookstore), adopts the 13C-NMR spectral method to determine.Should illustrate, also can adopt the method for 256 pages of this books " (i) random copolymer " record, adopt the IR spectroscopic methodology to determine.
[average grain diameter of mineral-type particulate]
Distribute with colloid Counter Multisizer (コ one Le one カ ウ one マ Le チ サ イ ザ one) gravimetry, will be with 50% particle diameter of directly representing as average grain diameter.Should illustrate, also can handle by image and obtain average grain diameter, perhaps obtain average grain diameter by the residue after with acid etc. the film that obtains being handled by biaxially oriented film.
[pore volume of mineral-type particulate]
According to the BET mode, adopt the method for JIS-K-1150 to measure.
[fold of goods film volume]
Be the polypropylene-based resin film of web-like after aging 12 hours will batching under 40 ℃ the atmosphere, visual this film volume judges that according to following standard corrugationless is arranged.
Zero: corrugationless
△: there is the part of corrugationless, but the poor yields of goods
*: all produce fold
[embodiment]
The present invention is described in detail below to adopt embodiment, but the present invention is not limited to the scheme of these embodiment, in the scope that does not break away from purport of the present invention, can suitably change.The composition of the sealant in proterties, composition, granulation condition, embodiment and the comparative example of the raw material that uses in embodiment and comparative example section A~G etc. is shown in table 1,2.
Table 1
The kind of inorganic, organic filler | Addition (wt%) | The 1st granulation condition | The 2nd granulation condition | ||||||||||||||||||
The prilling temperature condition (℃) | The filter mesh constitutes | Screw rod revolution (rpm) | Charger revolution (rpm) | The prilling temperature condition (℃) | The filter mesh constitutes | Screw rod revolution (rpm) | Charger revolution (rpm) | ||||||||||||||
Barrel 1 | Barrel 2 | Barrel 3 | Barrel 4 | Barrel 5 | Connector | Mould | Barrel 1 | Barrel 2 | Barrel 3 | Barrel 4 | Connector | Mould | |||||||||
Particle A | サイリシア 350 | 2.0 | 200 | 210 | 220 | 220 | 220 | 220 | 220 | 50/100 /50 | 300 | 20 | - | - | - | - | - | - | - | - | - |
Particle B | サイリシア350 | 2.0 | 200 | 210 | 220 | 220 | 220 | 220 | 220 | 50/100 /50 | 300 | 20 | 200 | 210 | 220 | 220 | 220 | 220 | 50/100/ 50 | 220 | 20 |
Particle C | サイリシア350 | 2.0 | 200 | 210 | 220 | 220 | 220 | 220 | 220 | 50/100 /50 | 220 | 20 | - | - | - | - | - | - | - | - | - |
Particle D | サイリシア350 | 2.0 | 200 | 210 | 220 | 220 | 220 | 220 | 220 | 50/100 /50 | 220 | 20 | 200 | 210 | 220 | 220 | 220 | 220 | 50/100/ 50 | 220 | 20 |
Particle E | サイリシア310P | 2.0 | 200 | 210 | 220 | 220 | 220 | 220 | 220 | 50/100 /50 | 300 | 20 | - | - | - | - | - | - | - | - | - |
Particle F | サイリシア420 | 2.0 | 200 | 210 | 220 | 220 | 220 | 220 | 220 | 50/100 /50 | 300 | 20 | - | - | - | - | - | - | - | - | - |
Particle G | CS18 | 2.0 | 200 | 210 | 220 | 220 | 220 | 220 | 220 | 50/100 /50 | 300 | 20 | - | - | - | - | - | - | - | - | - |
Table 2
The composition of sealant | |||||
The compounding of resin is than (wt%) | The content of basic material (wt%) | The addition of additive (wt%) | |||
FSX66E8 | BH180EL-2 | Glyceryl monostearate | Erucyl amide | ||
Embodiment 1 | A/B/ basic material=2.5/12.3/85.2 | 68.7 | 16.0 | 0.4 | 0.1 |
Embodiment 2 | C/B/ basic material=2.5/12.3/85.2 | 68.7 | 16.0 | 0.4 | 0.1 |
Embodiment 3 | G/F/B/ basic material=2.5/6.15/6.15/85.2 | 68.7 | 16.0 | 0.4 | 0.1 |
Embodiment 4 | A/B/ basic material=2.5/12.3/85.2 | 68.7 | 16.0 | 0.4 | 0.1 |
Embodiment 5 | A/B/ basic material=5.0/10.0/85.0 | 68.5 | 16.0 | 0.4 | 0.1 |
Embodiment 6 | A/B/ basic material=1.2/17.5/81.3 | 64.8 | 16.0 | 0.4 | 0.1 |
Comparative example 1 | B/ basic material=14.8/85.2 | 68.7 | 16.0 | 0.4 | 0.1 |
Comparative example 2 | A/ basic material=14.8/85.2 | 68.7 | 16.0 | 0.4 | 0.1 |
Comparative example 3 | A/E/ basic material=2.5/12.3/85.2 | 68.7 | 16.0 | 0.4 | 0.1 |
Comparative example 4 | C/D/ basic material=2.5/12.3/85.2 | 68.7 | 16.0 | 0.4 | 0.1 |
Comparative example 5 | A/B/ basic material=2.5/12.3/85.2 | 68.7 | 16.0 | 0.4 | 0.1 |
[making of anti-blocking agent masterbatch]
Compounding 0.15 weight portion イ Le ガ ノ ッ Network ス 1010 (the vapour Bart plants chemical company system), 0.15 weight portion イ Le ガ ホ ス, 168 (the vapour Bart plants chemical company system), 2.0 weight portions are as サ イ リ シ ア 350 (the シ リ シ ア of Fuji chemistry society system, the SiO 2 powder of mineral-type particulate in as the RW140EG (Sumitomo Chemical society system, ethylene contents 4.0 weight %, melt flow rate (MFR) 5.0g/10 branch) of propylene-ethylene copolymers powder; Average grain diameter 1.8 μ m, pore volume 1.60ml/g), making gross weight is 20kg, the peripheral speed 20m/ with the stirring vane top mixed 5 minutes second with the super mixer of 115L.
Use the double screw extruder (screw diameter 43mm φ, L/D:19.5) of 45mm φ then,, mixed material is only carried out 1 granulation, obtain particle A in that the revolution of screw rod, the revolution of charger are adjusted to respectively under the condition of 300rpm, 20rpm.In addition, after under the condition identical identical mixed material having been carried out granulation (the 1st granulation) with particle A, use identical double screw extruder, be adjusted to respectively at revolution under the condition of 220rpm, 20rpm and carry out granulation once more (the 2nd granulation), obtain particle B the revolution of screw rod, charger.On the other hand, use identical double screw extruder,,, obtain particle C an identical mixed material granulation 1 time in that the revolution of screw rod, the revolution of charger are adjusted to respectively under the condition of 220rpm, 20rpm.In addition, after under the condition identical identical mixed material having been carried out granulation (the 1st granulation), use identical double screw extruder with particle C, by with condition that the 1st time granulation is identical under carry out granulation (the 2nd granulation), obtain particle D.In addition, when the adjustment of mixed material, the mineral-type particulate is become サ イ リ シ ア 310P (the シ リ シ ア of Fuji chemistry society system, SiO 2 powder respectively; Average grain diameter 1.4 μ m), サ イ リ シ ア 420 (the シ リ シ ア of Fuji chemistry society system, SiO 2 powder; Average grain diameter 1.9 μ m, pore volume 1.25ml/g), by a granulation under the condition identical 1 time, obtain particle E, F with particle A.In addition, when the adjustment of mixed material, replace the mineral-type particulate and add organic based fine particles (system CS18 of Sumitomo Chemical society; The polymeric beads of average grain diameter 1.8 μ m), by a granulation under the condition identical 1 time, obtain particle G with particle A.Moreover, when the granulation of above-mentioned particle A~G, make the filter mesh constitute 50 orders/100 orders/50 orders, the temperature of the barrel with the 1st~the 4th, connector, mould is adjusted to 200 ℃, 210 ℃, 220 ℃, 220 ℃, 220 ℃, 220 ℃ (with reference to table 1) respectively.
[embodiment 1]
The making of<sealant 〉
Will be as the particle A 2.5 weight % of anti-blocking agent masterbatch, particle B 12.3 weight %, FSX66E8 as basic material (adopts the polypropylene-based resin of the Sumitomo Chemical society system of vapor phase method manufacturing, ethylene contents 2.5 weight %, 1-butene content 7.0 weight %, melt flow rate (MFR) 3.5g/10 branch) 68.7 weight %, BH180EL-2 (adopts the polypropylene-based resin of the Sumitomo Chemical society system of vapor phase method manufacturing, 1-butene content 25.0 weight %, melt flow rate (MFR) 3.0g/10 branch) 16.0 weight %, and monostearate monoglyceride 0.4 weight %, erucyl amide 0.1 weight % is melting mixing in the extruder (L/D:29) of 115mm φ, makes hot sealing layer.
The making of<basic unit 〉
FS2011DG3 (is adopted the polypropylene-based resin of the Sumitomo Chemical society system of vapor phase method manufacturing, ethylene contents 0.9 weight %, melt flow rate (MFR) 2.5g/10 branch) 97.89 weight %, S131 (adopts the polypropylene-based resin of the Sumitomo Chemical society system of vapor phase method manufacturing, ethylene contents 5.0 weight %, melt flow rate (MFR) 1.7g/10 branch) 1.26 weight %, and monostearate monoglyceride 0.10 weight %, polyoxyethylene (2) stearylamine monostearate 0.60 weight %, polyoxyethylene (2) stearylamine 0.15 weight % is at series connection extruder (the 1st section 175mm φ, L/D:17, the 2nd section 220mm φ, L/D:20) interior melting mixing is made basic unit.
The making of<film 〉
In extruder, respectively above-mentioned basic unit is formed to form and use the resin fusion, be controlled at laminated extruding in 3 layers of T pattern (branch manifold type, die orifice width 900mm, die gap 2.4mm) of 260 ℃ under this state with the quantity delivered of the extrusion capacity 126kg/H of the extrusion capacity 1980kg/H of basic unit, sealant with resin and sealant.At this moment, sealant in mould forms with resin by pack into the pad of wide 50mm of the two ends, the left and right sides of part, so that sealant is not laminated to the two ends, the left and right sides of basic unit.The molten resin extruded like this on 20 ℃ carry-over pinch rolls,, is drawn with the speed that 58.8m/ divides with wind speed 1050mmAq blowing with air knife,, obtain laminated resin sheet by cooling curing.Moreover, the laminated resin sheet that obtains as shown in Figure 2, the width of sealant is than the narrow about 50mm of the width of basic unit.After the sheet material that obtains then preheats with the roller that is heated to 108 ℃ to 130 ℃ successively respectively, be heated between 131 ℃ roller, 65.44m/ divides and the 242.12m/ branch gives speed difference by each roller speed is adjusted to, carry out 3.7 times longitudinal stretching, make its mitigation with the roller that is heated to 130 ℃ then.Then, after then the speed of dividing with 241.4m/ in 167.5 ℃ baking oven preheats the sheet material of longitudinal stretching, under 155 ℃ with the speed cross directional stretch to 10.7 of deformation velocity 1.39m/ second times, and then carry out the thermosetting deckle with making for 4.5 seconds it relax 8% 165 ℃ environment bottom, by cooling under 40 ℃ environment 1.5 seconds, make 2 kind of 3 layer film continuously with the gross thickness 20 μ m of the sequential laminating of sealant 0.8 μ m, the 18.4 μ m of basic unit, sealant 0.8 μ m.Then, Corona discharge Treatment is implemented on surface to the film of so continuous making, make the wetting tension of film surface reach 39mN/m, film after handling with coiling speed 241.4m/ bundling power taking corona under the environment that absolute humidity is controlled at more than the 8g/kgDryAir, what obtain width 6240mm, flow direction 29000m batches the film volume.And then under 40 ℃ environment with the film that batches volume keeping 12 hours, carry out after nature relaxes, be cut into the size of width 600mm, flow direction 4000m, obtain 70 Wound product films volume.The goods film volume that obtains does not have fold, can implement processing such as printing, bag well.In addition, adopt the characteristic of the film of the goods film volume that said method makes formation to estimate.Evaluation result is shown in table 3.In addition, roll up the film sample that downcuts ormal weight (about 1.0g) from the film that obtains, this film sample dry type is decomposed, after acid treatment, adopt plasma luminescence assay determination Al content, Al content is 34mg/kg as a result.
[embodiment 2]
In embodiment 1, when making sealant, use except replacing particle A the particle C, make goods film volume similarly to Example 1.The goods film that makes is rolled up corrugationless similarly to Example 1, can implement processing such as printing, bag well.In addition, adopt the characteristic of the film of the goods film volume that method similarly to Example 1 makes formation to estimate.Evaluation result is shown in table 3.
[embodiment 3]
In embodiment 1, when making sealant, replace particle A and use particle G, the part of particle B is replaced into particle F.In addition, make goods film volume similarly to Example 1.The goods film that makes is rolled up corrugationless similarly to Example 1, can implement processing such as printing, bag well.In addition, adopt the characteristic of the film of the goods film volume that method similarly to Example 1 makes formation to estimate.Evaluation result is shown in table 3.
[embodiment 4]
In embodiment 1, by the extrusion capacity of regulating the extruder that basic unit forms usefulness respectively and the extrusion capacity that sealant forms the extruder of usefulness, the thickness of the sealant of 2 kind of 3 layer film after the biaxial tension is become 0.6 μ m, simultaneously the thickness of basic unit is become 18.8 μ m (promptly becoming 2 kind of 3 layer film of totally 20 μ m of sealant sequential laminating of basic unit, the 0.6 μ m of sealant, the 18.8 μ m of 0.6 μ m).In addition, make goods film volume similarly to Example 1.The goods film that makes is rolled up corrugationless similarly to Example 1, can implement processing such as printing, bag well.In addition, adopt the characteristic of the film of the goods film volume that method similarly to Example 1 makes formation to estimate.Evaluation result is shown in table 3.
[embodiment 5]
When forming hot sealing layer, will be in the extruder of the 115mm φ identical as particle A 5.0 weight %, the particle B 10.0 weight % of anti-blocking agent masterbatch with embodiment 1, as FSX66E8 68.5 weight %, the BH180EL-216.0 weight % of basic material, and monostearate monoglyceride 0.4 weight %, erucyl amide 0.1 weight % melting mixing.In addition, make goods film volume similarly to Example 1.The goods film that makes is rolled up corrugationless similarly to Example 1, can implement processing such as printing, bag well.In addition, adopt the characteristic of the film of the goods film volume that method similarly to Example 1 makes formation to estimate.Evaluation result is shown in table 3.
[embodiment 6]
When forming hot sealing layer, will be in the extruder of the 115mm φ identical as particle A 1.2 weight %, the particle B 17.5 weight % of anti-blocking agent masterbatch with embodiment 1, as FSX66E8 64.8 weight %, the BH180EL-2 16.0 weight % of basic material, and monostearate monoglyceride 0.4 weight %, erucyl amide 0.1 weight % melting mixing.In addition, make goods film volume similarly to Example 1.The goods film that makes is rolled up corrugationless similarly to Example 1, can implement processing such as printing, bag well.In addition, adopt the characteristic of the film of the goods film volume that method similarly to Example 1 makes formation to estimate.Evaluation result is shown in table 3.
[comparative example 1]
In embodiment 1, when making sealant, use particle B except replacing particle A, the total compounding amount that makes particle B is 14.8 weight %.In addition, make goods film volume similarly to Example 1.The goods film that makes is rolled wrinkle, produces rough sledding in processing such as printing, bag.In addition, adopt the characteristic of the film of the goods film volume that method similarly to Example 1 makes formation to estimate.Evaluation result is shown in table 3.
[comparative example 2]
In embodiment 1, when making sealant, use particle A except replacing particle B, the total compounding amount that makes particle A is 14.8 weight %.In addition, make goods film volume similarly to Example 1.The goods film that makes is rolled wrinkle, produces rough sledding in processing such as printing, bag.In addition, adopt the characteristic of the film of the goods film volume that method similarly to Example 1 makes formation to estimate.Evaluation result is shown in table 3.
[comparative example 3]
In embodiment 1, when making sealant, use the particle E except replacing particle B, attempt making the film volume similarly to Example 1.But,, therefore can not make the worth film sample of estimating because generation is a large amount of by the bad foreign matter that causes of the dispersion of mineral-type particulate.
[comparative example 4]
In embodiment 1, when making sealant, use particle C except replacing particle A, replace particle B and use outside the particle D, make goods film volume similarly to Example 1.The goods film that makes is rolled wrinkle, produces rough sledding in processing such as printing, bag.In addition, adopt the characteristic of the film of the goods film volume that method similarly to Example 1 makes formation to estimate.Evaluation result is shown in table 3.
[comparative example 5]
In embodiment 1, except the heat fixation condition behind the film cross directional stretch being become under 171 ℃ environment 8% the mitigation of implementing 4.5 seconds, make goods film volume similarly to Example 1.Then, adopt the characteristic of the film of the goods film volume that method similarly to Example 1 makes formation to estimate.Evaluation result is shown in table 3.
Table 3
The performance of polypropylene-based resin film | |||||||||
μH40 | AR (second) | Haze value | Anti-corona property of initial stage | Anti-corona continuation | Fusing sealing (disqualification rate: %) | Heat seal strength (N/15mm) | Wetting tension (mN/m) | Goods | |
Embodiment | |||||||||
1 | 0.8 | 3.0 | 2.2 | 6 |
6 grades | 0 | 3.8 | 39 | ○ |
|
0.75 | 2.8 | 2.1 | 6 |
6 grades | 0 | 3.5 | 39 | ○ |
|
0.65 | 7.5 | 3.0 | 6 |
6 grades | 0.05 | 3.4 | 39 | ○ |
|
0.61 | 8.0 | 2.0 | 6 |
6 grades | 0 | 3.0 | 39 | ○ |
|
0.70 | 1.9 | 2.8 | 6 |
6 grades | 0 | 3.2 | 39 | ○ |
|
0.97 | 3.4 | 2.2 | 6 |
6 grades | 0 | 3.4 | 39 | ○ |
Comparative example 1 | 1.40 | 4.5 | 2.0 | 5 |
5 grades | 20 | 4.0 | 39 | × |
Comparative example 2 | 0.74 | 1.3 | 3.2 | 5 |
5 grades | 10 | 3.4 | 39 | × |
Comparative example 3 | Can not measure | Can not measure | Can not measure | Can not measure | Can not measure | Can not measure | Can not measure | Can not measure | Can not measure |
Comparative example 4 | 1.0 | 1.5 | 2.7 | 6 |
6 |
6 | 3.6 | 39 | △ |
Comparative example 5 | 0.78 | 2.0 | 6.0 | 6 |
6 grades | 0.1 | 3.8 | 39 | ○ |
[effect of the film of embodiment]
As shown in Table 3, the film of embodiment is owing to μ H40, AR, haze value satisfy condition of the present invention, and therefore anti-corona property, the transparency well do not produce fold on the film volume, and the sealing that fuses is good.In contrast to this, the μ H40 of the film of comparative example 1 is big, the condition of discontented unabridged version invention, and the film volume is gone up and is produced fold, the fusing sealing is extremely bad, the AR value of the film of comparative example 2,4 is little, and the condition of discontented unabridged version invention produces fold on the film volume, the fusing sealing is bad, the transparency of the film of comparative example 5 is poor, the condition of the discontented unabridged version invention of haze value, and content seems not distinct during packing.
Therefore polypropylene resin laminated film of the present invention is applicable to the packing purposes of raw and fresh food owing to have the characteristic of aforesaid excellence.
Claims (18)
1. polypropylene resin laminated film, this polypropylene resin laminated film is at the laminated sealant that has based on polyolefin resin of tow sides based on the basic unit of polypropylene-based resin, thickness is that 10 μ m are above, less than 70 μ m, and haze value is more than 0.4%, below 5.0%
Wherein: the polypropylene-based resin that constitutes basic unit and sealant adopts vapor phase method to form, and satisfies following formula (1), (2),
(1) coefficient of kinetic friction of measuring under 40 ℃ atmosphere is more than 0.2, below 1.1,
(2) air exhaust index is more than 1.8 seconds, below 10.0 seconds, this air exhaust index be with 2 film overlaies, from when decompression until time from emptying air between the film.
2. polypropylene resin laminated film according to claim 1, wherein: at least basic unit has been carried out biaxial tension.
3. polypropylene resin laminated film according to claim 1, wherein: in the whole layer of laminate film, contain more than the 15mg/kg, the Al of not enough 150mg/kg.
4. polypropylene resin laminated film according to claim 1, wherein: basic unit is formed by propylene-ethylene copolymers, and ethylene contents is that 0.5 weight % is above, less than 1.5 weight % in this propylene-ethylene copolymers.
5. polypropylene resin laminated film according to claim 1, wherein: sealant is 1/60~1/3 with respect to the ratio of whole layers thickness of laminate film.
6. polypropylene resin laminated film according to claim 1, wherein: in basic unit and sealant, be added with anti-clouding agent.
7. polypropylene resin laminated film according to claim 6, wherein: be equipped with in covering under the state of peristome of container of 50 ℃ of warm water, the bond area of the dew after taking out under the atmosphere in room temperature after placing 30 minutes under 5 ℃ the atmosphere be below 1/4 of integral body.
8. polypropylene resin laminated film according to claim 1, wherein: use the point of a knife angle is adjusted to 60 degree, the point of a knife design temperature is adjusted to 390 ℃ fusing sealer, the disqualification rate when making the fusing sealing bag of film with 120 bags/minute jet velocity under 370 ℃ of point of a knife temperature is below 5%.
9. polypropylene resin laminated film according to claim 1, wherein: at 140 ℃ down with adding 1kg/cm in 1 second
2Pressure make between the sealant heat fusing bonding after, the intensity when peeling off these heat fusing bonding portions with 180 degree is more than the 1.5N/15mm, below the 6.0N/15mm.
10. polypropylene resin laminated film according to claim 1, wherein: the wetting tension on sealant surface is more than the 35mN/m, below the 45mN/m.
11. polypropylene resin laminated film according to claim 1, wherein: the resin that forms sealant is its melt flow rate (MFR) to be adjusted to 1.5g/10 divide resin above, that 9.0g/10 divides or their mixture.
12. polypropylene resin laminated film according to claim 1, wherein: in forming the polyolefin type resin layer of sealant, be added with more than the average grain diameter 1.0 μ m, less than 12.0 μ m and pore volume are more than the 1.0ml/g, the mineral-type particulate of not enough 2.0ml/g.
13. polypropylene resin laminated film according to claim 6, wherein: anti-clouding agent and with in polyoxyethylene alkyl amine type anti-clouding agent, polyoxyethylene alkyl amine fatty acid ester type anti-clouding agent, the fatty glyceride type anti-clouding agent more than at least 2 kinds.
14. polypropylene resin laminated film according to claim 6, wherein: the anti-corona dosage in whole layers of laminate film is that 0.2 weight % is above, less than 1.5 weight %.
15. the manufacture method of a polypropylene resin film is the manufacture method that is used to make the described polypropylene resin laminated film of claim 1, wherein: comprise
By from a plurality of extruders, adopting coetrusion that polypropylene-based resin and polyolefin resin are melt extruded, form the polypropylene resin laminated filming operation that does not stretch,
Will be by not stretching of obtaining of this filming operation the polypropylene resin laminated longitudinally and horizontal biaxial tension operation of biaxial tension;
Satisfy following important document (a)~(c):
(a) above-mentioned filming operation is adopt to add the propylene-ethylene copolymers of mineral-type particulate and granulation 1 time, add the propylene-ethylene copolymers, polypropylene-based resin of mineral-type particulate and granulation 2 times and form the operation of sealant,
(b) above-mentioned filming operation is to adopt propylene-ethylene copolymers to form basic unit, simultaneously the ethylene contents in this propylene-ethylene copolymers is adjusted to that 0.5 weight % is above, the operation of less than 1.5 weight %,
(c) above-mentioned biaxial tension operation is longitudinally and laterally to carry out heat fixation after the biaxial tension, with the adjustment of above-mentioned heat fixation is simultaneously more than 160 ℃, the operation of 170 ℃ of less thaies.
16. the manufacture method of polypropylene-based resin film according to claim 15, wherein: the rotary body that employing is rotated with the rotary speed more than the 100rpm, below the 500rpm carries out the granulation in the above-mentioned filming operation.
17. polypropylene resin laminated film, this polypropylene resin laminated film is at the laminated sealant that has based on polyolefin resin of tow sides based on the basic unit of polypropylene-based resin, thickness is that 10 μ m are above, less than 70 μ tm, and haze value is more than 0.4%, below 5.0%, wherein:
The polypropylene-based resin that constitutes basic unit and sealant adopts vapor phase method to form; Simultaneously
Form with resin laminated by in the T pattern, making the basic unit that melt extrudes by the 1st extruder form the sealant that melt extrudes with resin, by the 2nd extruder, making is basic unit and the laminated laminated resin sheet that does not stretch of the sealant narrower than this base width, laminated biaxial tension of resin of the not stretching that will make then and forming;
Satisfy following formula (1), (2),
(1) coefficient of kinetic friction of measuring under 40 ℃ atmosphere is more than 0.2, below 1.1,
(2) air exhaust index is more than 1.8 seconds, below 10.0 seconds, this air exhaust index be with 2 film overlaies, from when decompression until time from emptying air between the film.
18. polypropylene resin laminated film according to claim 17, wherein: as above-mentioned T pattern, utilize sealant form with resin pass through partly about two ora terminalis the T pattern of pad is installed.
Applications Claiming Priority (9)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2006023878 | 2006-01-31 | ||
JP2006-023878 | 2006-01-31 | ||
JP2006023878 | 2006-01-31 | ||
JP2006175609 | 2006-06-26 | ||
JP2006175609 | 2006-06-26 | ||
JP2006-175609 | 2006-06-26 | ||
JP2006-217385 | 2006-08-09 | ||
JP2006217385A JP2008030425A (en) | 2006-01-31 | 2006-08-09 | Propylenic resin laminated film and its manufacturing method |
JP2006217385 | 2006-08-09 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN101024318A true CN101024318A (en) | 2007-08-29 |
CN101024318B CN101024318B (en) | 2010-12-01 |
Family
ID=39120326
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN2006101723588A Active CN101024318B (en) | 2006-01-31 | 2006-12-18 | Polypropylene resin laminated film and its manufacturing method |
Country Status (3)
Country | Link |
---|---|
JP (1) | JP2008030425A (en) |
CN (1) | CN101024318B (en) |
TW (1) | TWI436889B (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102597145A (en) * | 2009-08-24 | 2012-07-18 | 东洋纺织株式会社 | Adhesive film |
CN104130507A (en) * | 2014-07-25 | 2014-11-05 | 桐乡市振华新型包装材料有限公司 | Anti-fog plastic film |
CN106081344A (en) * | 2016-06-20 | 2016-11-09 | 广东宝佳利彩印实业有限公司 | The preparation method of a kind of plastic containers containing soy sauce are the most swollen encapsulating closing lid film |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5755975B2 (en) * | 2011-09-01 | 2015-07-29 | 昭和電工パッケージング株式会社 | Battery exterior material and lithium secondary battery |
JP7089864B2 (en) * | 2017-02-15 | 2022-06-23 | 松本油脂製薬株式会社 | Anti-fog polypropylene film |
EP4046934A4 (en) * | 2019-11-19 | 2023-11-08 | Toppan Inc. | Method for manufacturing packaging body, film for packaging material, and laminated film and packaging material comprising the same |
-
2006
- 2006-08-09 JP JP2006217385A patent/JP2008030425A/en active Pending
- 2006-12-18 CN CN2006101723588A patent/CN101024318B/en active Active
-
2007
- 2007-08-27 TW TW096131629A patent/TWI436889B/en active
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102597145A (en) * | 2009-08-24 | 2012-07-18 | 东洋纺织株式会社 | Adhesive film |
CN102597145B (en) * | 2009-08-24 | 2014-06-18 | 东洋纺织株式会社 | Adhesive film |
CN104130507A (en) * | 2014-07-25 | 2014-11-05 | 桐乡市振华新型包装材料有限公司 | Anti-fog plastic film |
CN106081344A (en) * | 2016-06-20 | 2016-11-09 | 广东宝佳利彩印实业有限公司 | The preparation method of a kind of plastic containers containing soy sauce are the most swollen encapsulating closing lid film |
Also Published As
Publication number | Publication date |
---|---|
TW200909211A (en) | 2009-03-01 |
TWI436889B (en) | 2014-05-11 |
CN101024318B (en) | 2010-12-01 |
JP2008030425A (en) | 2008-02-14 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN101024318B (en) | Polypropylene resin laminated film and its manufacturing method | |
CN107848680B (en) | Boiling is packed for polypropylene-based sealing film and the laminated body using it | |
CN101809082B (en) | Resin composition, molding resin composition prepared by using the same, laminates, and process for the production of laminates | |
CN101688005A (en) | Polypropylene molded article, sheet-like polypropylene molded article, and method for production of polypropylene thermally molded article | |
JP4609464B2 (en) | Polypropylene-based resin laminated film and method for producing the same | |
CN1933970B (en) | Polypropylene type laminated film and package using it | |
CA2638871C (en) | Plastic bags and zippers manufactured of a polymeric material containing inorganic filler | |
SA517380908B1 (en) | Maleic anhydride grafted lldpe having high melt index | |
JP2024050552A (en) | Polyethylene-based resin multilayer film, and vapor-deposited film, laminate and package using the same | |
CN101787157B (en) | Pe film SS comprising interpolymer using 3 -substituted C4-10 alkene and single site catalyst | |
CN113365824A (en) | Polypropylene resin multilayer film | |
TW202204158A (en) | Biaxially oriented polypropylene resin film and package using same | |
EP2452974A1 (en) | Polymeric composition, method for producing non-stretched film, non-stretched film, heat-sealing material, and packaging material | |
JP2012515820A (en) | PEM1B film ZN / CR | |
JP2023158008A (en) | Biaxially oriented polypropylene-based resin film, and package using the same | |
JP4240076B2 (en) | Polypropylene-based resin laminated film and method for producing the same | |
JP2003291282A (en) | Film and package for packaging fruit and vegetables | |
EP3034291A1 (en) | Method to improve making of heat sealable biaxially oriented films | |
CN109562612A (en) | Stacked film, laminated film and packing container | |
EP3695964A1 (en) | Recyclable black plastic food tray | |
JP2000219786A (en) | Film | |
JP2009051134A (en) | Polypropylene resin laminated film and its production method | |
WO2023176481A1 (en) | Masterbatch pellets | |
WO2023176480A1 (en) | Polyolefin resin film roll | |
WO2023176482A1 (en) | Method for producing polyolefin resin film |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant |