CN1911651A - Laminated film of polypropylene and molded body - Google Patents
Laminated film of polypropylene and molded body Download PDFInfo
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- CN1911651A CN1911651A CN 200610115431 CN200610115431A CN1911651A CN 1911651 A CN1911651 A CN 1911651A CN 200610115431 CN200610115431 CN 200610115431 CN 200610115431 A CN200610115431 A CN 200610115431A CN 1911651 A CN1911651 A CN 1911651A
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Abstract
The invention provides a polypropylene type laminated film for holograms which allows easy formation of irregularities constituting a hologram by embossing and has excellent secondary processability, e.g. bag processing by heat sealing. The laminated film consists of a surface layer of a propylene type copolymer overlying at least one side of a substrate layer of a polypropylene type resin, and the propylene type copolymer has a peak top temperature, Tp, of the maximum peak of 70-100 DEG C, with a half-value width of the peak of lower than 10 DEG C, in the elution temperature-elution amount curve by the continuous temperature-raising elution fractionation. Irregularities constituting a hologram are formed on the surface of the surface layer by embossing.
Description
Technical field
The present invention relates to novel laminated film of polypropylene as hologram film (hologram film) use.
Background technology
The hologram film owing to have luminous ornamental for iridescence, can be used for strip of paper used for sealing, illustration, the gift wrap of books, the package bag of good decorative property etc., also can be used for advertisement in addition, shows purposes etc.In addition, owing to be provided with metallic reflector (for example AM aluminum metallization), protective clear layer (for example evaporation zinc sulphide) by evaporation on the face that constitutes hologram, the hologram film becomes the film of high-decoration, high surface protection.
These hologram films by the driving fit exposure method of usability luminescent material, on the flat film surface, apply fine embossing method for processing etc. and obtain, but, use the embossing method for processing in recent years mostly because photosensitive material is more expensive.
For example, as the method for making the hologram film, proposition has pattern is copied to method on the substrate that polyester is provided with 2 μ m carbamate layers, promptly will press under the state be attached on the substrate manufacture method (patent documentation 1) of the hologram film that this substrate is cooled off as the hot-rolling that duplicates roller.
In addition, also propose to have and on the surface of the double shaft extensioning film that constitutes by polyester, carry out fine embossing processing (formation hologram) and metallic reflector is set and the hologram film that forms.Record in the method the temperature-sensitive adhesive linkage also is set on film, can be used as copy film and use (with reference to patent documentation 2).
But, by the hologram film that said method etc. obtains, which kind of film all be with polyester as base material, carrying out back processing, for example use this film, wait by heat-sealing and carry out bag and add man-hour, also there is room for improvement in the secondary operations that is difficult to seal etc.
In addition, propose to have the film-forming method (with reference to patent documentation 3) that on the surface that constitutes by polypropylene-based resin, constitutes hologram.This method is utilized the chill roll with hologram embossment master, the homo-polypropylene of fusion is pushed cooling, at the film forming hologram that forms simultaneously.
But, this method, at the film forming hologram that forms simultaneously, even for example will obtain also having as film under the situation of double shaft extensioning film of intensity carrying out back processing, natural hologram can disappear, and has room for improvement aspect processability.
In addition, propose to have the film (patent documentation 4) of on the film surface that constitutes by polypropylene, implementing fine embossing processing.It is concrete that to propose to have thickness be that the surface roughness of one side of the film of 0.03～0.2mm is 0.1～1 μ m, the polypropylene-based resin film processed by embossing.
But, above-mentioned film, existence can only obtain the problem that thickness is the above film of 0.03mm.In addition, the surface roughness of above-mentioned film is that 0.1 μ m is above, more coarse, is to be purpose with the coating that reaches good print and bonding agent, is not that to form formation the concavo-convex of hologram on film surface be purpose to reach.Moreover, disclosing by fusing point in the embodiment of patent documentation 4 is the single thin film that 141 ℃ polypropylene-based resin constitutes, but this film, duplicate in use under the situation of the dandy roll that the hologram of micro concavo-convex uses, be difficult on the surface of this film, form the concavo-convex of formation hologram, have room for improvement.
[patent documentation 1] Japanese kokai publication hei 3-53924 communique
[patent documentation 2] Japanese kokai publication sho 62-191872 communique
[patent documentation 3] Japanese kokai publication hei 3-68982 communique
[patent documentation 4] Japanese kokai publication hei 10-315325 communique
Summary of the invention
The object of the present invention is to provide a kind of laminated film of polypropylene, it is concavo-convex that it constitutes hologram on laminated film of polypropylene is not that resin by coating or lamination photosensitive material one class forms, but directly form, and the secondary workability excellence of processing etc. by the bag of heat-sealing by embossing processing.
In addition, provide a kind of laminated film of polypropylene, it is provided with metallic reflector or protective clear layer by evaporation on above-mentioned laminated film of polypropylene, and hologram does not disappear thus, can carry out thermoplastic resin membrane's lamination at least on the film one side.
Also provide a kind of above-mentioned film etc. is sealed the formed body that obtains.
The inventor studies intensively in order to achieve the above object repeatedly.It found that: be a kind of laminate film that will have the propylene copolymers of specific crystallinity distribution as superficial layer, utilize embossing processing to form on this superficial layer and constitute the concavo-convex of hologram, achieve the above object, thereby finish the present invention.
Promptly, a kind of laminated film of polypropylene of the present invention, it is characterized in that: will be the superficial layer that the half breadth at 70～100 ℃ and this peak constitutes less than 10 ℃ propylene copolymers by the summit temperature (Tp) of maximum peak in the eluting temperature-elution amount curve of continuous intensification elution fractionation method (TREF), at at least one superimposed layer of the substrate layer that constitutes by polypropylene-based resin and constitute, by embossing processing, on the surface of this superficial layer, be formed with the concavo-convex of formation hologram.
In addition, this laminated film of polypropylene of the present invention is formed with on the concavo-convex above-mentioned superficial layer that constitutes hologram from the teeth outwards, and going back lamination, thickness is arranged is following metallic reflector or protective clear layer of 50～500nm.
In addition, plural layers of the present invention have the thermoplastic resin membrane with the further lamination of mode that hologram is disappeared on above-mentioned laminated film of polypropylene.
Formed body of the present invention obtains by above-mentioned film is sealed.
Laminated film of polypropylene of the present invention, constitute as the laminate film that superficial layer uses by the propylene copolymers that will have specific crystallinity distribution, therefore, can easily directly form the concavo-convex of formation hologram on this film surface by embossing processing, it is irregular not produce thickness.In addition, this laminate film owing to use polypropylene-based resin, even under the situation by the heat-sealing secondary operations, also can access the high formed body of hot strength (below, be called heat seal strength) of heat-sealing portion.Owing to there is not the irregular film of thickness; be formed with on the concavo-convex superficial layer that constitutes hologram so can access; during by evaporations such as aluminium further lamination metal reflecting layer or protective clear layer; obtain the dhering strength and the evaporation excellence of vapor-deposited film and TPO laminate film, and the hologram film of aesthetic appearance excellence.In addition; on the laminated film of polypropylene that is provided with metallic reflector or protective clear layer; the plural layers of multilayer thermoplastic resin film are not only to have the secondary workability of heat-sealing, and the film with feature of thermoplastic resin, can access the good formed body of aesthetic appearance and packing character.
Description of drawings:
Fig. 1 is the eluting temperature-elution amount curve at the TREF of the propylene copolymers of the superficial layer use of embodiment 1.
Fig. 2 is eluting temperature-elution amount curve of the TREF of the propylene copolymers that uses of the superficial layer of comparative example 1.
Fig. 3 is eluting temperature-elution amount curve of the TREF of the propylene copolymers that uses of the superficial layer of embodiment 2.
Fig. 4 is used for the skeleton diagram of an example of the equipment of enforcement embossing processing (hologram pattern) on superficial layer for expression.
Symbol description:
1 expansion portion; 2 preheat rolls; 3 rubber rollers; 4 embossing roller for machining; 5 sided corona treatment; 6 reeling ends
The specific embodiment
On the one side at least of the substrate layer that constitutes by polypropylene-based resin, the superficial layer that lamination is made of the propylene copolymers with specific crystallinity distribution, forming laminate film, form the concavo-convex of formation hologram on the superficial layer of this laminate film, promptly is laminated film of polypropylene of the present invention.
In the present invention, there is no particular limitation for the polypropylene-based resin that substrate layer uses, and can be the random or block copolymer of single polymers, propylene and other a spot of for example alpha-olefin below 10%, for example ethene, 1-butylene, 1-hexene, 4-methyl-1-pentene, 1-octene, the 1-decene etc. of propylene.Wherein preferably using five unit composition ratio is that 0.88～0.98 Noblen, ethylene contents are that following propylene-ethylene copolymer of 1.0 quality % or butene content are the propylene-butylene copolymer below 3%.In addition, above-mentioned polypropylene-based resin can use the material of polymerization in the presence of ziegler-natta catalyst, metallocene catalyst etc., can also mix and use a plurality of materials.
Among the present invention, the fusing point of the polypropylene-based resin that above-mentioned substrate layer uses is not particularly limited, the propylene copolymers that uses with superficial layer keeps balance, and add man-hour at the enforcement embossing, film itself does not produce by the processing preheat temperature and causes mist white, and outward appearance is good, and the thermal contraction that adds the film in man-hour diminishes, be preferably more than 150 ℃, more preferably more than 155 ℃, preferred especially more than 158 ℃.The upper limit of the fusing point of the polypropylene-based resin that substrate layer uses is not particularly limited, and considers in the industrial production to obtain easily, is limited to 165 ℃ on the fusing point.In addition, as polypropylene-based resin, when using a plurality of mixture, the fusing point of each polypropylene-based resin is preferably more than 150 ℃.In addition, when using mixture, with content in the mixture at most the fusing point of the polypropylene-based resin of (main component) be benchmark, can with the fusing point of following propylene copolymers relatively.
In the present invention, the melt flow rate of the polypropylene-based resin that above-mentioned substrate layer uses also is not particularly limited, but considers common system film, and preferred use is at the material of 1.0～8.0g/10 minute scope.
In addition, in the polypropylene-based resin that above-mentioned substrate layer uses, in the scope of not damaging purpose of the present invention, can be added on the antioxidant, weather resisting agent, lubrication prescription, antistatic agent, antifoggant, chlorine agent for capturing, nuclear agent, antiblocking agent, the organic-inorganic filler that use in the common polypropylene.
In the present invention, at the superficial layer of at least one superimposed layer of substrate layer, be 70～100 ℃, and the half breadth at this peak constitute less than 10 ℃ propylene copolymers by the summit temperature (Tp) of the maximum peak that utilizes continuous intensification elution fractionation method (TREF) to measure.The present invention can access the hologram film of aesthetic appearance excellence by carry out embossing processing on this superficial layer.
In addition, in the present invention, so-called above-mentioned continuous intensification elution fractionation method (TREF) is to measure the method for the crystallinity distribution of thermoplastic resins such as polyolefin.Its assay method, at first, in the post that the inert carrier with diatomite, silicon grain (silica beads) etc. uses as filler, injection is dissolved in the sample solution that o-dichlorohenzene obtains with the test portion polyolefin, the temperature of post is descended, make test portion attached to the filler surface.Thereafter, Yi Bian o-dichlorohenzene is flowed in this post, column temperature is risen, detection is in the polyolefinic concentration of wash-out at each temperature.Then, by temperature in polyolefinic elution amount (quality %) and the post of this moment (℃) value, obtain eluting temperature-elution amount curve, measure polyolefinic crystallinity and distribute.Eluting temperature uprises along with the easier crystallization of wash-out composition, so the relation of the elution amount (quality %) by obtaining eluting temperature and polymer can learn that the crystallinity of polymer distributes.
In the said determination method, the decrease speed of column temperature is adjusted to the needed speed of crystallization under crystallinity contained in the test portion polyolefin set point of temperature partly, in addition, the rate of climb of column temperature is adjusted to the speed that test portion dissolving at each temperature can finish, and this column temperature decrease speed and the rate of climb can determine in advance by experiment.The decrease speed of column temperature is decided to be the scope below 5 ℃/minute, and the rate of climb of column temperature is decided to be the scope below 40 ℃/minute.
Superficial layer at least one superimposed layer of substrate layer of the present invention, the so-called layer that is processed to form hologram by embossing, by in eluting temperature-elution amount curve of measuring by above-mentioned continuous intensification elution fractionation method (TREF), the summit temperature of maximum peak (Tp) is that 70～100 ℃ propylene copolymers constitutes.The Tp of aforesaid propylene analog copolymer is less than under 70 ℃ the situation, and it is soft that propylene copolymers itself becomes, and traumatic resistance reduces, and impairs the attractive in appearance of hologram pattern, and is therefore not preferred.In addition, when Tp surpassed 100 ℃, the crystallinity of propylene copolymers uprised, and was processed to form the concavo-convex relatively difficulty that constitutes hologram by embossing, can not obtain the good hologram of outward appearance, and is therefore not preferred.That is, when using Tp to surpass 100 ℃ propylene copolymers, set higherly if embossing adds the temperature in man-hour, then may carry out processing to a certain degree, but the embossing processing temperature is when being high temperature, laminated film of polypropylene itself is shunk or fusion by heat, the pattern distortion of hologram, outward appearance worsens.Moreover, in these cases, because the influence of thermal contraction takes place to relax on film, so not preferred.Consider the productivity ratio of film, the outward appearance of hologram, Tp is preferably at 75～95 ℃, more preferably at 80～90 ℃.
In addition, in the present invention, the aforesaid propylene analog copolymer that superficial layer uses, its Tp is at 70～100 ℃, and the half breadth of maximum peak is important less than 10 ℃.Half breadth as maximum peak is the width (Fig. 1 represents the elution curve of propylene copolymers of the present invention) of half eluting temperature highly of expression summit.That is, this half breadth is narrow, then represents the crystallinity narrowly distributing of propylene copolymers.
In the present invention, superficial layer uses the propylene copolymers of this half breadth less than 10 ℃ crystallinity narrowly distributing.Think that the embossing that is undertaken describing in detail below adds man-hour, superficial layer uniformly softening or fusion by using such propylene copolymers.Therefore, the micro concavo-convex that constitutes hologram forms uniformly at the thickness direction of whole superficial layer and film, can access the more excellent hologram film of outward appearance.In addition, when on such hologram film, also being provided with metallic reflector, can access hologram film with distincter colour.
In the present invention, the half breadth of propylene copolymers is more than 10 ℃ the time, and the crystallinity of propylene copolymer distributes wide, the softening unevenly or fusion along with the embossing processing temperature.Its result, concavo-convex being difficult to that constitutes hologram forms on superficial layer, produces coming off of hologram etc., makes outward appearance not good, and be therefore not preferred.Lower limit to half breadth is not particularly limited, but considers from the industrial viewpoint that obtains easily, is more than 2 ℃.Consider embossing processability, outward appearance etc., more preferably 2～7 ℃ of the half breadths of aforesaid propylene analog copolymer.
In addition, the fusing point of the propylene copolymers that above-mentioned superficial layer uses is not particularly limited, but the fusing point of the polypropylene-based resin that preferably uses than above-mentioned substrate layer, low 15～65 ℃.The fusing point of aforesaid propylene analog copolymer satisfies above-mentioned scope, adds man-hour at embossing, and laminate film is peeled off from metal system dandy roll, preheat roll etc. easily, can duplicate more clearly to constitute the concavo-convex of hologram, and it is better that thickness and precision becomes.In addition, in the laminate film that obtains, oozing out of noncrystalline composition is few, can access the better film of outward appearance.Laminated film of polypropylene of the present invention has excellent outward appearance, utilize embossing processing to constitute the concavo-convex easy formation of hologram, and can not produce uneven thickness, in order to achieve the above object, low 20～55 ℃ of the fusing point of the polypropylene-based resin that the fusing point of the propylene copolymers that this superficial layer uses preferably uses than substrate layer, more preferably low 25～50 ℃.In addition, poor about this fusing point, when the polypropylene-based resin that substrate layer uses is made of a plurality of mixtures, polypropylene-based resin with main component is a benchmark, when the propylene copolymers that superficial layer uses was made of a plurality of mixtures, the fusing point of the propylene copolymers of the maximum peak of being measured by TREF with expression was a benchmark.
In the present invention, the aforesaid propylene analog copolymer that superficial layer uses, if the half breadth at the summit temperature of above-mentioned maximum peak (Tp) and this peak satisfies above-mentioned scope, just there is no particular limitation, can be the copolymer that more than one copolymerization such as propylene and other alpha-olefin, for example ethene, 1-butylene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene obtains.Wherein preferred propylene and other alpha-olefin carry out more than one random copolymerization and the binary, ternary and the polynary random copolymer that obtain.Moreover, also can mix these two or more copolymers.The aforesaid propylene analog copolymer preferably uses the copolymer that utilizes metallocene catalyst polymerisation to obtain.
In the present invention, in the aforesaid propylene analog copolymer that superficial layer uses, if satisfy above-mentioned maximum peak at 70～100 ℃, and the half breadth at this peak then can add other propylene copolymers not influence the ratio of these scopes less than 10 ℃ condition.That is, in the aforesaid propylene analog copolymer that superficial layer uses,,, add other following propylene copolymers of 40 mass parts not influence the mode of above-mentioned scope with respect to this propylene copolymers of 100 mass parts.Wherein, with respect to the above-mentioned PP type copolymer of 100 mass parts, preferred other propylene copolymers that adds 1～40 mass parts, this propylene copolymers, in the eluting temperature-elution amount curve that obtains by continuous intensification elution fractionation method (TREF), the summit temperature of maximum peak (Tp) is at 35～50 ℃, and the half breadth at this peak is less than 10 ℃.Satisfy other propylene copolymers of above-mentioned condition by interpolation, can carry out embossing processing at low temperatures, prevent that the film mist is white, thermal contraction also diminishes in addition.By adding above-mentioned other propylene copolymers, on superficial layer, more clearly duplicate the concavo-convex of formation hologram, so preferred.
In addition, the melt flow rate of the aforesaid propylene analog copolymer that superficial layer uses is not particularly limited, and considers the situation of common molding, preferably uses the melt flow rate of 1.0～16.0g/10 minute scope.
In the propylene copolymers that superficial layer uses, not damage the scope of purpose of the present invention, add the antioxidant, weather resisting agent, lubrication prescription, antistatic agent, antifoggant, chlorine agent for capturing, nuclear agent, antiblocking agent, the organic-inorganic filler that use in the common polypropylene.Wherein, in being provided with the laminated film of polypropylene of metallic reflector described later, the heat-sensitive resin layer is set also on metallic reflector, under situation about using, in this superficial layer, preferably contains lubrication prescription as copy film.Owing to have lubrication prescription, can obtain good replicability.
In the present invention, by the laminate film that above-mentioned substrate layer and superficial layer constitute, can be 2 layer films that on the one side of substrate layer, have superficial layer, also can be 3 layer films that on the two sides of substrate layer, have superficial layer.In order to make substrate layer and superficial layer lamination, can adopt the coetrusion that utilizes multiple layers of molds, coextrusion to form the resin of each layer, after also can adopting the film that forms a layer, fusion forms suitable row lamination (inline lami) method of the resin and the lamination of other layer, certainly, since carry out vapor deposition treatment, printing treatment or with the lamination process of other film, can carry out sided corona treatment, flame treatment, plasma treatment etc. to the film that obtains as required.
Among the present invention, there is no particular limitation for the thickness of superficial layer, but preferably above-mentioned laminate film integral thickness 2～50%.In addition, along with embossing processing, the thickness that produces slightly on the laminated film of polypropylene is irregular, and the concavo-convex integral thickness with respect to this laminated film of polypropylene that is obtained by embossing processing is very little, and it is irregular therefore can to ignore this thickness.That is, among the present invention, the thickness proportion of above-mentioned superficial layer can be calculated by the laminate film of implementing the embossing first being processed.Among the present invention, the ratio of superficial layer can obtain the embossing excellent in workability in 2～50% scope, the heat seal strength height, and can not produce the white laminated film of polypropylene of mist.
The integral thickness of above-mentioned laminate film suitably determines according to use, if consider molding method, processability, market demands, is 10 μ m～100 μ m.
Above-mentioned laminate film can be no extension film, uniaxial extension film, double shaft extensioning film, wherein, as described later, in order to make the film filming, to obtain the film of high fracture strength, is preferably double shaft extensioning film.
In the present invention, the laminate film by above-mentioned substrate layer and above-mentioned superficial layer constitute is not particularly limited, but in order to make the film filming, obtains the contour film of fracture strength, is preferably double shaft extensioning film.In addition, film thickness also can suitably determine according to use according to above-mentioned, by making double shaft extensioning film, can access the film less than the thickness of 60 μ m more than or equal to 10 μ m.Like this by making double shaft extensioning film,, also can become and have high-intensity film even less than the film of the thickness of 100 μ m.
Among the present invention, when above-mentioned laminate film is made double shaft extensioning film, after the resin coextrusion with each layer use, twin shaft extension method or twin shaft extension method one by one when can adopt tentering method (tenter), the perhaps method of extending by the twin shaft of tubulose (tubular) method.In addition, can adopt the polypropylene-based resin that substrate layer is used to melt extrude, be shaped to laminar after, extend in the single shaft direction, then in the above, the propylene copolymers that superficial layer is used melt extrudes, with the upwardly extending method in side of the direction approximate vertical of above-mentioned unidirectional extension.
In the present invention, when above-mentioned laminate film was made double shaft extensioning film, extension ratio was preferably gone up at film flow direction (following note is made MD) and is extended 2.0～10.0 times, goes up in the direction vertical with this direction (following note is made TD) and extends 2.0～10 times.
Laminated film of polypropylene of the present invention on the surface of the superficial layer of above-mentioned laminate film, is processed to form by embossing and constitutes the concavo-convex of hologram.If form hologram on superficial layer, just there is no particular limitation for this concavo-convex size, for the iridescence pattern of distincter performance hologram uniqueness, preferably forms the concavo-convex of shorter than wavelength of visible light at least size on the surface of this superficial layer.Particularly, concavo-convex difference of height is 10～1000nm, more preferably 50～800nm.Superficial layer is owing to having the concavo-convex of shorter than wavelength of visible light at least size, so form the hologram film with distinct iridescence pattern.In addition, during with alignment diagram surface roughness (Ra) expression, its scope is 5～500nm, preferred 25～400nm.Its result by the evaporation metal reflecting layer, can access distincter hologram film.Certainly, in order to improve outward appearance, when forming the hologram of various patterns, on above-mentioned superficial layer, can contain the part beyond the surface roughness of part beyond above-mentioned scope concavo-convex or above-mentioned scope.The concavo-convex state of film surface can be measured by scanning type probe microscope (SPM).
In the present invention, be processed to form the concavo-convex method that constitutes hologram by embossing on the surface of the superficial layer of laminate film, there is no particular limitation, can form laminate film, and this film of heating before batching carries out embossing processing.In addition, launch, can heat, carry out embossing processing in case will coil into the laminate film of roller shape.By adopting these methods, can on the superficial layer that is extended by twin shaft, implement embossing processing, obtain the high film of intensity.
In the present invention,, on laminate film, carry out embossing and add man-hour, at the superficial layer that makes laminate film under the softening or molten condition, utilize metal to neutralize the line roller for machining and rubber roller pushes, form the hologram pattern at this superficial layer by said method.
Among the present invention, Fig. 4 represents to utilize said method, implements an example (Fig. 4 is for implementing the example that embossing is processed to laminate film being coiled into the material that the roller shape get) of the equipment of embossing processing (hologram pattern) on the superficial layer of above-mentioned laminate film.These equipment preferably are made of expansion portion 1, preheat roll 2, rubber roller 3, embossing roller for machining 4, sided corona treatment 5, reeling end 6, carry out embossing and add man-hour, send laminate film by reeling end 1, after heating with 2 pairs of films of preheat roll, with embossing roller for machining 4 and rubber roller 3 extruding.
In the present invention, use equipment as Fig. 4, on the superficial layer of above-mentioned laminate film, form the concavo-convex method that constitutes hologram, thickness according to laminate film is selected, in above-mentioned suitable film thickness scope, the speed (roller rotary speed) of sending film is 30～80m/min, and the temperature of the preheat roll that is provided with before dandy roll is preferably 100 ℃～180 ℃.In addition, create conditions down above-mentioned, the temperature of metal system dandy roll 3 is preferably 30～100 ℃.The temperature of this embossing roller for machining is set at above-mentioned scope, and on the surface of the superficial layer of above-mentioned laminate film, even constitute the micro concavo-convex of hologram, it is irregular also can not to produce thickness on film, can be easy to formation.
In the present invention, the embossing pattern on the embossing roller for machining uses and can will constitute the concavo-convex pattern that copies on the laminate film of hologram.Laminated film of polypropylene of the present invention is used for superficial layer in order to have the propylene copolymers that specific crystallinity distributes, can be with the roughly the same form of the pattern form of embossing roller for machining 4, and on the concavo-convex surface that copies to this superficial layer.In addition, owing to the thermal contraction of the film that adds man-hour is little, can also improve mouldability.The embossing roller for machining can directly be processed the hologram pattern on roller, also the version that obtains at the holographic pattern of processing on the metal forming can be fitted on the embossing roller for machining and use.
In the present invention, form on the concavo-convex laminated film of polypropylene that constitutes hologram from the teeth outwards, for carry out vapor deposition treatment, printing treatment or with the lamination process of other film, after embossing processing, can utilize known method such as flame treatment, plasma treatment, sided corona treatment, carry out surface treatment.
In the present invention, form to constitute the concavo-convex laminated film of polypropylene of hologram from the teeth outwards, because substrate layer, superficial layer be made of polypropylene-based resin, the processing and forming by heat-sealing etc. obtains formed body easily.For example as formed body, the handling ease of the heat-sealing (fusing sealing) of the heat-sealing of half folding, fusing sealing or use multi-disc film etc. is carried out.Such formed body; under the overlapping state of superficial layer and superficial layer, carry out; but laminated film of polypropylene of the present invention; under the situation of following metallic reflector of lamination not or protective clear layer; use the lower resin of fusing point; so can seal at low temperatures, become the big film of intensity of heat-sealing portion.
Among the present invention, going back lamination on the superficial layer of above-mentioned laminated film of polypropylene has metallic reflector or protective clear layer, becomes the protective layer of protection hologram pattern.Certainly, metallic reflector or protective clear layer are forming the concavo-convex surperficial superimposed layer that constitutes hologram.In this case, on superficial layer, preferably by raising wettability of the surface such as sided corona treatment.Particularly, carry out sided corona treatment etc., make that the wetting index on superficial layer surface is 44～35dyn.
Among the present invention, on the face of the hologram that forms above-mentioned laminated film of polypropylene, metallic reflector is arranged owing to go back lamination; protection hologram pattern; avoid causing the hologram disappearance, and the pattern of hologram appears in one's mind more brightly, can improve iridescence by friction and the coating of transparent adhesive.Specify the method for the above-mentioned metallic reflector of lamination for example, for example can pass through the metal of AM aluminum metallization, gold, silver, copper and these alloy etc., carry out lamination, wherein, AM aluminum metallization is industrial preferred.In addition, consider pattern, the hologram characteristic of hologram, the metallic reflection layer thickness is 5～500nm.In addition, among the present invention, by using the described propylene copolymers of above-mentioned first aspect, metallic reflector is stronger with the adaptation of the face that forms hologram, so preferred.
In addition, can also the lamination protective clear layer on the superficial layer of above-mentioned laminated film of polypropylene.By the lamination protective clear layer, have the transparency, can hologram be disappeared because of friction or transparent adhesive etc., can carry out the lamination processing of film.Specify the method for the above-mentioned protective clear layer of lamination for example, for example, carry out lamination by evaporation zinc sulphide or in order to prevent that film is coloured to yellow and uses the material that contains a spot of magnesium in zinc sulphide, silicon oxide compounds etc.In addition, the thickness of this protective clear layer is identical with metallic reflector, considers aesthetic appearance, evaporation mouldability, is 5～500nm.
Among the present invention,, can adopt generally well-known method, particularly, adopt vacuum vapour deposition, sputtering method, ion plating etc. as the method for lamination metal reflecting layer or protective clear layer.
Among the present invention, in order to keep various functions, above-mentioned laminated film of polypropylene can become disappears hologram, keep the hologram pattern, go back the plural layers that lamination has the thermoplastic resin membrane.So-called reservation hologram pattern, the multilayer thermoplastic resin film, for example at laminated film of polypropylene not when lamination metal reflecting layer or protective clear layer, on the face of not implementing hologram processing, can the multilayer thermoplastic resin film.In addition, when lamination metal reflecting layer or protective clear layer, can be at least on the face of metallic reflector or protective clear layer, multilayer thermoplastic resin film again.
In the present invention, so-called above-mentioned thermoplastic film, just there is no particular limitation if form the thermoplastic resin membrane, for example be to be the TPO film of representative, to be polyester film, nylon film, many ethlyene dichlorides film of representative with the PETG with polypropylene and polyethylene, can be single thin film, also can be the multilayer class film with heat-sealing function etc.Can be not have the film that extends or be extended in addition.Wherein, if consider recovery, the aspect of discarding, polypropylene film is favourable in the thermoplastic film of lamination.These thermoplastic resin membranes can implement printing, metal evaporation before lamination.
Among the present invention, above-mentioned thermoplastic resin membrane suitably selects according to the purposes of using.For example in laminated film of polypropylene, in order further to improve hear resistance, when not lamination metal reflecting layer or protective clear layer, can be chosen on the face of not implementing hologram processing the plural layers that form by known method applying polyester film.
In addition, at the film of laminated film of polypropylene superimposed layer metallic reflector or protective clear layer, himself can seal, in order further to improve heat seal strength, and can be with the face superimposed layer of TPO film at metallic reflector or protective clear layer.In addition, for intensity, the hear resistance that improves film, can the lamination polyester film.Under this situation, preferably at the face that seals (part in the bag of formed body) superimposed layer TPO film, its opposite face directly contacts with heat-sealing portion, in order to improve hear resistance, at its opposite face superimposed layer polyester film.
In the present invention, the method for multilayer thermoplastic film also can utilize coating adhesive make it lamination dried laminating, make the known method such as extruding layer platen press of molten resin lamination, carry out lamination and make the hologram pattern not disappear.The hologram film of such laminate film can freely be used for this film whole or a part of formed body (for example being called major part).Particularly, evaporation metal reflecting layer etc., hot-working can be carried out in the film two sides that the thermoplastic film that can seal on the two sides is fitted, and the iridescence of hologram is distincter, becomes the formed body that has very much feature.
In the present invention, about the thermoplastic film of lamination, can lamination have implemented the film that prints in advance.By printing film and hologram combination, hologram pattern and printing overlap, and can access film and formed body thereof with aesthetic appearance.
In the present invention, on above-mentioned laminated film of polypropylene, according to the purposes of using, the multilayer thermoplastic resin film, the plural layers that obtain for example can improve the secondary workability (mouldability) of heat-sealing etc., characteristic by thermoplastic resin improves hot-working stability, covering property of fragrance, uses as packaging material.
Embodiment
Below in order to specify the present invention, enumerate embodiment, but the present invention is not limited to these
Embodiment.
(1) Measurement of melting point
Utilize the DSC device DSC6200 of Seiko electronics society system, under the following conditions, measure.
Test portion amount: about 5mg
Atmosphere gas: nitrogen (flow 20ml/ minute)
Temperature conditions: 230 ℃ kept down after 10 minutes, cooled to 30 ℃ with 10 ℃/minute, continued with 10 ℃ of/minute intensification, measured the heat absorption state that fuses this moment, with its peak temperature as fusing point.
(2) transparency (turbidity value)
Based on JIS Z1712, measure the turbidity value of 1 film.
(3) the maximum peak temperature (Tp) of intensification elution fractionation method (TREF), the mensuration of half breadth
Utilize the automatic TREF device SSC-7300ATREF of セ Application シ ユ one science society system, measure according to following condition.
Solvent: o-dichlorohenzene
Flow velocity: 150ml/ hour
Programming rate: 4 ℃/hour
Detector: infrared detector
Measure terminal number: 3.41 μ m
Post: 30mm Φ * 300mm
Filler: Chromosorb (Chromosorb) P (trade name)
Concentration: 1g/120mm
Injection rate: 100ml
Under this situation, under 145 ℃, sample solution is imported in the post, slowly be cooled to 10 ℃ with 2 ℃/hour speed, make the test portion resin adsorption behind the filler surface, with above-mentioned condition column temperature is heated up, pick up the survey device with infrared ray and measure the resin concentration of separating out at each temperature, obtain elution curve (Fig. 1, Fig. 2, Fig. 3).Thus, from 1/2 the height at the temperature (Tp) of maximum peak and peak obtain half breadth (℃).
Embodiment 1
(manufacturing of biaxial stretched polypropylene film)
On substrate layer, use MFP=3g/10 branch, 160 ℃ of common twin shafts of fusing point to extend with acrylic resin (primepolymer.co. system trade name F-300SP).On a side top layer, use same materials, as antiblocking agent, to cooperate average grain diameter be the calcium carbonate (ball tail calcium system trade name CUBE-18BHS) of 2 μ to account for 0.1% mode.At a side top layer, the so-called superficial layer that is processed to form hologram by embossing, to use MFP=8g/10 branch, fusing point be 125 ℃, obtain under TREF Tp=80 ℃, half breadth are 5 ℃ random PP (Japan polypropylene corporation system trade name WFX4), as propylene copolymers.
These resins are filled into substrate layer respectively to be used in the extruder with extruder, each top layer, under 250 ℃ forming temperature, extrude, extrusion capacity ratio in extruder, being set at respect to substrate layer extrusion capacity 18 each top layer extrusion capacity is that 1 molten resin utilizes chill roll to cool off, and making gross thickness thus is 3 layers of thin slice of 1mm.Then in the vertical, under 120 ℃ temperature, extend this thin slice with the speed difference between 5 times of rollers, continuation is in being called the baking oven of stenter, under 180 ℃ temperature, 10 times of horizontal expansions, batch it with coiling machine, obtaining layer thickness is that 20 μ m, each skin depth are the laminated film of polypropylene of 1 μ m.
(being processed to form hologram) by embossing
The CZ-RY that utilizes Beijing to create scientific and technological limited commercial firm system is that the hologram processing machine carries out embossing processing (Fig. 4).The film of sending from expansion portion 1, be set at heating on 145 ℃ the preheat roll 2, in hologram processing, to on the AL paper tinsel, process the surface that version is attached to the embossing roller for machining 4 that is set at 40 ℃ by the figuratum hologram of mint-mark, the material of Xing Chenging has the face of the PP type copolymer of laminated film of polypropylene to contact with lamination thus, at this moment, with rubber roller 3 extruding, the pattern of version is copied on the film.Then, by batching, be made into the hologram film with reeling end 6.About the quality of the hologram that obtains, measure the concavo-convex of hologram and arithmetic average rugosity (Ra) according to the methods below, and use visual judgement.In addition, the version of using is to represent the concavo-convex version that is 260nm, Ra as 70nm of the iridescence of hologram.
(utilizing the mensuration of concavo-convex, arithmetic average rugosity (Ra) of the laminated film of polypropylene of scanning type probe microscope (SPM))
Device: Digital Instruments system NanoscopeIIIa and phase difference extendermodule
Condition determination: utilize and rap Mode A FM (Tapping Mode AFM) observation HeightImage and Phase Image.
Scan Size 70μ～5μ
Probe: single crystalline Si manufacturing probe (model: NCH-10V)
From the image that obtains thus, measure height profile with n=5, measure the concavo-convex and Ra of hologram.
(outward appearance of hologram is judged)
About the judgement of hologram appearing, at first measure hologram processing version with SPM, the concavo-convex of version processed in investigation.Then, identical patterns part to the film that carries out hologram processing with same processing version, measure and to utilize the concavo-convex of hologram film that SPM measures equally, the concavo-convex ratio of the concavo-convex and hologram of processing version the concavo-convex/hologram film of processing version concavo-convex=0.3～3.0 scope in, in addition, judge that by visual outward appearance the degree that obtains bright-coloured iridescence pattern is expressed as the judgement of ◎, zero, △ in turn.In addition, this concavo-convex ratio be more than 0.3 or 3.0 above scopes beyond be expressed as *.
(the traumatic resistance evaluation of hologram)
Preparation cuts into 30cm on vertical bearing of trend, 2 of the films of 20cm on horizontal bearing of trend, and this external application セ ロ テ one プ (registration mark) etc. are a slice film fixedly, makes above face through hologram processing is, thereby constitutes lower film.Use セ ロ テ one プ (registration mark) etc. to fix another sheet film again, make above the face that carried out hologram processing on the area of diameter 10cm circle is, thereby constitute upper film.On lower film, year load onto portion's film, give the load of 4.6kg, on the position of par direction between 20cm, wipe repeatedly and close 5 times.Carry out the turbidity value of the front and back of this operation and measure, wipe the difference close the back and to wipe the turbidity value before closing such as followingly carried out for 4 stages and estimate with said method.
◎: more than or equal to 0 less than 1.5%
Zero: more than or equal to 1.5 less than 3.0%
△: more than or equal to 3.0 less than 6.0%
*: more than or equal to 6%
The evaluation result of the laminated film of polypropylene that obtains like this is shown in table 1.
Embodiment 2
Except among the embodiment 1, be used for the acronal of hologram machined surface (superficial layer), with respect to embodiment 1 employed random PP (Japan polypropylene system trade name WFX4) 100 mass parts, Tp=37 ℃ of 30 mass parts of mixing, the propylene copolymers (Mitsui Chemicals system trade name Off マ one XM7070) of 10 ℃ of half breadths, 70 ℃ of fusing points in addition, carry out (Fig. 3) similarly to Example 1.The Tp of the maximum peak when mixing in addition is identical with embodiment 1 with half breadth.The evaluation result of the laminated film of polypropylene that so obtains is shown in table 1.
Embodiment 3
Homogeneous (homo) PP (Sumitomo Chemical system trade name FLX80E5) of use MFR=8g/10 minute on substrate layer, 160 ℃ of fusing points, using the raw material identical with substrate layer on a side top layer, is that to make its concentration be 0.1% for the calcium carbonate (ball tail calcium system trade name CUBE-40KAS) of 4 μ as AB agent cooperation average grain diameter.The opposing party forms the propylene copolymers use material similarly to Example 1 on the top layer (superficial layer) of hologram, fill it in the extruder separately, in the extrusion capacity ratio, after layer structure be set at 1/8/1, make it to contact with chill roll, with film speed 30m/ minute cooling film, batch with coiling machine again, obtaining gross thickness is that 60 μ m, each skin depth are the no extension film of 6 μ m.Afterwards except that carrying out hologram processing similarly to Example 1, with embodiment 1 identical carrying out.The evaluation result of the laminated film of polypropylene that so obtains is shown in table 1.
Embodiment 4
In embodiment 1, to use Tp=90 ℃, half breadth as the employed propylene copolymers of hologram machined surface (superficial layer) be that 5 ℃, fusing point are 135 ℃ the propylene copolymers (Japan polypropylene (strain) system trade name WFW4), carry out similarly to Example 1.The evaluation result of the laminated film of polypropylene that so obtains is shown in table 1.
Comparative example 1
In embodiment 1, to use Tp=92 ℃ shown in Figure 2, half breadth as the employed propylene copolymers of hologram machined surface (superficial layer) be 15 ℃ the propylene copolymers (Sumitomo Chemical system trade name FS3611), carry out similarly to Example 1.The evaluation result of the laminated film of polypropylene that so obtains is shown in table 1.
Comparative example 2
In embodiment 1, to use Tp=115 ℃, half breadth as the employed propylene copolymers of hologram machined surface (superficial layer) be 8 ℃ the propylene copolymers (サ Application ア ロ マ-system trade name PC412A), carry out similarly to Example 1.The evaluation result of the laminated film of polypropylene that so obtains is shown in table 1.
Comparative example 3
In embodiment 1, to use Tp=48 ℃, half breadth as the employed propylene copolymers of hologram machined surface (superficial layer) be 9 ℃ the propylene copolymers (Mitsui Chemicals system trade name XM7080), carry out similarly to Example 1.The evaluation result of the laminated film of polypropylene that so obtains is shown in table 1.
Comparative example 4
In embodiment 3, as the propylene copolymers shown in the employed propylene copolymers use of hologram machined surface (superficial layer) comparative example 3, carry out similarly to Example 3.The evaluation result of the laminated film of polypropylene that so obtains is shown in table 1.
Table 1
| Substrate layer | Propylene copolymers | Hologram is estimated | Traumatic resistance is estimated | |||||||
| Fusing point | Peak-peak Tp | Maximum peak | Fusing point | Film is concavo-convex | Version/film | Outward appearance is judged | Ra | The △ turbidity | Judge | |
| Half breadth | Concavo-convex ratio | |||||||||
| ℃ | ℃ | ℃ | ℃ | n m | 4 stages were estimated | nm | ％ | 4 stages were estimated | ||
| Embodiment 1 | 160 | 80 | 5 | 125 | 250 | 1.04 | ◎ | 65 | 0.5 | ◎ |
| Embodiment 2 | ↑ | 80 | 5 | 125 | 240 | 1.08 | ○ | 58 | 1.5 | ○ |
| Embodiment 3 | ↑ | 80 | 5 | 125 | 238 | 1.09 | ○ | 55 | 1.8 | ○ |
| Embodiment 4 | ↑ | 90 | 5 | 135 | 248 | 1.05 | ◎ | 62 | 0.5 | ◎ |
| Comparative example 1 | ↑ | 92 | 15 | 135 | 135 | 1.92 | △ | 32 | 1.5 | ○ |
| Comparative example 2 | ↑ | 115 | 8 | 156 | 67 | 3.88 | × | 17 | 0.3 | ○ |
| Comparative example 3 | ↑ | 48 | 9 | 80 | 240 | 1.08 | ○ | 49 | 6.2 | × |
| Comparative example 4 | ↑ | 48 | 9 | 80 | 238 | 1.08 | ○ | 49 | 6.9 | × |
Embodiment 5
On embodiment 1 resulting laminated film of polypropylene (hologram film), by following method lamination metal reflecting layer.
(the lamination processing of metallic reflector)
Utilize the system ZZ-1800 of Shanghai dawn vacuum equipment Co., Ltd high vacuum vapor deposition equipment for making film to carry out the lamination of metallic reflector.The thickness of this lamination carries out the film thickness monitoring of evaporation thing by the thickness theoretical amount of relative thin membrane area.For example at 1cm
2During the aluminium-vapour deposition layer of film superimposed layer 100nm, theoretical necessary amount is 0.29g, adds the 0.33g of 10% increment, implements vapor deposition treatment continuously, sets by machinery, makes evaporation 1cm
2The time full consumption 0.3g, thus thickness is controlled.In addition, measure with method shown in following, be 40nm about the thickness of actual lamination.
(the thickness practical measurement of metallic reflector)
The mensuration utilization of the thickness of actual lamination is measured thickness by the lubber-line of the absorption photometric generation of fluorescent X-ray shown below.Promptly use the fluorescent X-ray device of OXFORD system Lab-X3000, carry out the strength detection of the specific X ray of corresponding element about the evaporation thing, the lamination mould that the standard sample of the known in advance lamination thickness of use makes and the lubber-line of specific X ray intensity are measured the evaporation thickness.
(dhering strength of metallic reflector or protective clear layer and laminated film of polypropylene is measured)
Use セ ロ テ one プ (registration mark) of the ニ チ バ Application system of commercially available wide 15mm, on by the face of lamination, in the mode of complete driving fit, applying 20cm left and right sides metallic reflector or protective clear layer on the film longitudinal direction.Make it to peel off then, state is peeled off in visualization, carries out for 4 stages and estimates at once.
◎: metallic reflector and peeling off fully of transparent evaporation layer do not have on the band side.
Zero: area peels off below 5% on the band side.
△: area peels off below 30% more than 5% on the band side.
*: 30% of area peels off on the band side.
The evaluation result of the laminated film of polypropylene that obtains thus is shown in table 2.
(the lamination ocular estimate of metallic reflector or protective clear layer (evaporation come off evaluation))
Film is cut out 10cm * 10cm at the every 10M of flow direction, use Lasertec Co., Ltd system laser microscope 1LM21 type is observed the above evaporation of 0.2mm Φ and is come off, and measures its number.With the mean value that n=10, (flow direction 100M) measure, it is done the ocular estimate of 3 stages.Evaluation result is shown in table 2.
Zero: 0.0～below 1.0
△: below 1.0～2.0
*: more than 2.0
Embodiment 6
Use device similarly to Example 5, on the laminated film of polypropylene that carries out hologram processing that embodiment 1 obtains, carry out the transparent evaporation of zinc sulphide.The thickness of the zinc sulphide that obtains is measured the characteristic X-ray intensity of the zinc of fluorescent X-ray similarly to Example 5, by the lubber-line that utilizes known film to obtain, measures the thick thickness of evaporation of zinc sulphide evaporation.The evaluation result of the PP type film that so obtains is shown in Table 2.
Embodiment 7
On the laminated film of polypropylene that carries out hologram processing that obtains at embodiment 3, beyond the method lamination metal evaporation layer identical, carry out similarly to Example 5 with embodiment 5.The evaluation result of the laminated film of polypropylene that so obtains is shown in Table 2.
Embodiment 8
On the laminated film of polypropylene that carries out hologram processing that obtains at embodiment 1, usefulness method is similarly to Example 5 carried out the lamination of metallic reflector, and the evaporation thickness is set at 400nm, and actual thickness is beyond the 420nm, to carry out similarly to Example 5.The evaluation result of the laminated film of polypropylene that so obtains is shown in Table 2.
Comparative example 5
On the laminated film of polypropylene that obtains at comparative example 1, utilize beyond the method lamination metal reflecting layer similarly to Example 5, carry out similarly to Example 5.The results are shown in the table 2.
Comparative example 6
On the laminated film of polypropylene that obtains at comparative example 3, utilize beyond the method lamination metal reflecting layer similarly to Example 5, carry out similarly to Example 5.The evaluation result of the PP type film that so obtains is shown in Table 2.
Table 2
| Metallic reflector/and the evaluation of transparent evaporation layer | ||||||
| Kind | The measured value of laminated thickness | Peel off area | Estimate | Shortcoming point number | The lamination ocular estimate | |
| nm | ％ | 4 stages were estimated | 100cm 2 | 3 stages were estimated | ||
| Embodiment 5 | | 40 | 0 | ◎ | 0 | ○ |
| Embodiment 6 | | 120 | 0 | ◎ | 0 | ○ |
| Embodiment 7 | Aluminium | 41 | 0 | ◎ | 0 | ○ |
| Embodiment 8 | Aluminium | 420 | 0 | ◎ | 0 | ○ |
| Comparative example 5 | Aluminium | 42 | 8 | △ | 1.6 | △ |
| Comparative example 6 | Aluminium | 43 | 31 | × | 1.8 | △ |
Embodiment 9
Extend polyolefin film (Suntox Co. in commercially available nothing, Ltd system CPP trade name LU02#20) on, the solution of the dual liquid type dry laminate agent that use will be made of common bonding agent, curing agent after with organic solvent diluting, be coated with into the thickness of 1～2 μ m, on the face of not implementing hologram processing with the resultant film adhered laminated film of polypropylene that obtains at embodiment 1 (hologram film).Then, be the mode of the inboard of bag there not to be the polyolefin film of extension stromatolith, utilize following method to seal processing (fusing sealing processing), obtain formed body, estimate.
(formed body manufacture method)
About formed body, utilize common prosperity printing (strain) fusing sealer PP-500, be 360,400,450 ℃ with the design temperature of fusing sword, 120 times/minute (120shot/minute) carries out bag, makes formed body.Following table is shown the evaluation of formed body.
(evaluation of formed body (mensuration of fusing sealing intensity))
Utilize the Autograph of the system AGS-D of Shimadzu Seisakusho Ltd. type, carry out the fusing sealing is cut out the tension test of the wide rectangular sample of 15mm, from fusing sealing fracture the time intensity, carry out 5 benchmark, measure in 5 bag of 25 benchmark again with identical bag product, with the mean value that obtains as the fusing sealing intensity.In addition, mean value visual by outward appearance and the fusing sealing intensity is judged as follows to formed body.
◎: the fusing sealing does not have striped, distortion, burr, seals well, and the intensity under the seal temperature that fuses separately is more than the 25N/15mm.
Zero: the fusing sealing does not have striped, distortion, burr, seals well, and the intensity under the seal temperature that fuses separately is below the 15 above 25N/15mm.
△: produce any situation of striped, distortion, burr, the intensity under the fusing seal temperature separately is below the 15 above 25N/15mm.
*: produce any situation of striped, distortion, burr, and the intensity under the fusing seal temperature separately is below the 15N.
The evaluation result of the formed body of the laminated film of polypropylene that obtains thus is shown in table 3.
On the metallic reflection aspect except the hologram film that obtains at embodiment 5 with metallic reflector, extend polyolefin film (Suntox Co. at commercially available twin shaft, Ltd system trade name PA20#20) goes up and implement the film that printing obtains, with embodiment 9 used dry lamination agent applying Printing Department and metallic reflection face, beyond its opposing face applying no extension film similarly to Example 9, carry out similarly to Example 9.The evaluation result of the formed body of the laminated film of polypropylene that so obtains is shown in Table 3.
Embodiment 11
Except replacing the biaxial stretched polypropylene film of the film shown in the embodiment 10, beyond the commercially available polyester film of fitting (Japan spinning trade name E5100) #12, carry out similarly to Example 9.The evaluation result of the formed body of the laminated film of polypropylene that so obtains is shown in table 3.
Embodiment 12
The metallic reflection face of the film that embodiment 5 is obtained is made formed body as outside the bag with the method shown in the embodiment 9, and its evaluation is carried out similarly to Example 9.The evaluation result of the formed body of the PP type lamination that so obtains is shown in Table 3.
Table 3
| Laminate film | Formed body is estimated | |||||||
| 360 ℃ of seal temperatures | 400 ℃ of seal temperatures | 450 ℃ of seal temperatures | ||||||
| The hologram page lamination | The opposite face lamination | Intensity (N/15mm) | 4 stages were estimated | Intensity (N/15mm) | 4 stages were estimated | Intensity (N/15mm) | 4 stages were estimated | |
| Embodiment 9 | Do not have | CPP | 32 | ◎ | 31 | ◎ | 25 | ○ |
| | OPP | CPP | 31 | ◎ | 29 | ◎ | 26 | ○ |
| Embodiment 11 | Polyester | CPP | 33 | ○ | 35 | ○ | 43 | ◎ |
| Embodiment 12 | Do not have | Do not have | 26 | ◎ | 27 | ◎ | 25 | ○ |
Claims (4)
1. laminated film of polypropylene is characterized in that:
To be the superficial layer that the half breadth at 70～100 ℃ and this peak constitutes less than 10 ℃ propylene copolymers by the summit temperature (Tp) of maximum peak in the eluting temperature-elution amount curve of continuous intensification elution fractionation method (TREF), at at least one superimposed layer of the substrate layer that constitutes by polypropylene-based resin and constitute
By embossing processing, on the surface of this superficial layer, be formed with the concavo-convex of formation hologram.
2. laminated film of polypropylene as claimed in claim 1 is characterized in that:
Be formed with from the teeth outwards on the concavo-convex superficial layer that constitutes hologram, metallic reflector or protective clear layer that further laminated thickness is 5～500nm constitute.
3. plural layers is characterized in that:
In claim 1～2, on each described laminated film of polypropylene, further constitute with the mode multilayer thermoplastic resin film that does not make the hologram disappearance.
4. formed body is characterized in that:
Obtain by each described film in the heat-sealing claim 1～3.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005230339 | 2005-08-09 | ||
| JP2005230339 | 2005-08-09 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN 200610115431 Pending CN1911651A (en) | 2005-08-09 | 2006-08-09 | Laminated film of polypropylene and molded body |
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| TW (1) | TW200720077A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102926285A (en) * | 2012-11-09 | 2013-02-13 | 东莞市胜景光学材料有限公司 | Process for producing polymer embossing papers |
| CN114425897A (en) * | 2022-04-06 | 2022-05-03 | 广东德冠薄膜新材料股份有限公司 | Moldable metal-platable polypropylene film and preparation method and application thereof |
-
2006
- 2006-07-21 TW TW095126772A patent/TW200720077A/en unknown
- 2006-08-09 CN CN 200610115431 patent/CN1911651A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102926285A (en) * | 2012-11-09 | 2013-02-13 | 东莞市胜景光学材料有限公司 | Process for producing polymer embossing papers |
| CN114425897A (en) * | 2022-04-06 | 2022-05-03 | 广东德冠薄膜新材料股份有限公司 | Moldable metal-platable polypropylene film and preparation method and application thereof |
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| TW200720077A (en) | 2007-06-01 |
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